Part XIII - Manufacturing Industries

Français

Chapter 82 - Metal Processing and Metal Working Industry
GENERAL PROFILE The metal smelting and refining industry processes metal ores and scrap metal to obtain pure metals. The metal working industries process metals in order to manufacture machine components, machinery, instruments and tools which are needed by other industries as well as by the other different sectors of the economy. Various types of metals and alloys are used as starting materials, including rolled stock (bars, strips, light sections, sheets or tubes) and drawn stock (bars, light sections, tubes or wire). Basic metal processing techniques include: · smelting and refining of metal ores and scrap · casting molten metals into a given shape (foundry) · hammering or pressing metals into the shape of a die (hot or cold forging) · welding and cutting sheet metal · sintering (compressing and heating materials in powder form, including one or more metals) · shaping metals on a lathe. A wide variety of techniques are used to finish metals, including grinding and polishing, abrasive blasting and many surface finishing and coating techniques (electroplating, galvanizing, heat treatment, anodizing, powder coating and so forth).

SMELTING AND REFINING
Pekka Roto* *Adapted from the 3rd edition, Encyclopaedia of Occupational Health and Safety.

In the production and refining of metals, valuable components are separated from worthless material in a series of different physical and chemical reactions. The end-product is metal containing controlled amounts of impurities. Primary smelting and refining produces metals directly from ore concentrates, while secondary smelting and refining produces metals from scrap and process waste. Scrap includes bits and pieces of metal parts, bars, turnings, sheets and wire that are off-specification or worn-out but are capable of being recycled (see the article ―Metal reclamation‖ in this chapter).

Overview of Processes
Two metal recovery technologies are generally used to produce refined metals, pyrometallurgical and hydrometallurgical. Pyrometallurgical processes use heat to separate desired metals from other materials. These processes use differences between oxidation potentials, melting points, vapour pressures, densities and/or miscibility of the ore components when melted. Hydrometallurgical technologies differ from pyrometallurgical processes in that the desired metals are separated from other materials using techniques that capitalize on differences between constituent solubilities and/or electrochemical properties while in aqueous solutions. Pyrometallurgy During pyrometallic processing, an ore, after being beneficiated (concentrated by crushing, grinding, floating and drying), is sintered or roasted (calcined) with other materials such as baghouse dust and flux. The concentrate is then smelted, or melted, in a blast furnace in order to fuse the desired metals into an impure molten bullion. This bullion then undergoes a third pyrometallic process to refine the metal to the desired level of purity. Each time the ore or bullion is heated, waste materials are created. Dust from ventilation and process gases may be captured in a baghouse and are either disposed of or returned to the process, depending upon the residual metal content. Sulphur in the gas is also captured, and when concentrations are above 4% it can be turned into sulphuric acid. Depending upon the origin of the ore and its residual metals content, various metals such as gold and silver may also be produced as by-products. Roasting is an important pyrometallurgical process. Sulphating roasting is used in the production of cobalt and zinc. Its purpose is to separate the metals so that they can be transformed into a water-soluble form for further hydrometallurgical processing. The smelting of sulphidic ores produces a partially oxidized metal concentrate (matte). In smelting, the worthless material, usually iron, forms a slag with fluxing material and is converted into the oxide. The valuable metals acquire the metallic form at the converting stage, which takes place in converting furnaces. This method is used in copper and nickel production. Iron, ferrochromium, lead, magnesium and ferrous compounds are produced by reduction of the ore with charcoal and a flux (limestone), the smelting process usually taking place in an electric furnace. (See also the Iron and steel industry chapter.) Fused salt electrolysis, used in aluminium production, is another example of a pyrometallurgical process. The high temperature required for the pyrometallurgical treatment of metals is obtained by burning fossil fuels or by using the exothermic reaction of the ore itself (e.g., in the flash

smelting process). The flash smelting process is an example of an energy-saving pyrometallurgical process in which iron and sulphur of the ore concentrate are oxidized. The exothermic reaction coupled with a heat recovery system saves a lot of energy for smelting. The high sulphur recovery of the process is also beneficial for environmental protection. Most of the recently built copper and nickel smelters use this process. Hydrometallurgy Examples of hydrometallurgical processes are leaching, precipitation, electrolytic reduction, ion exchange, membrane separation and solvent extraction. The first stage of hydrometallurgical processes is the leaching of valuable metals from less valuable material, for example, with sulphuric acid. Leaching is often preceded by pre-treatment (e.g., sulphating roasting). The leaching process often requires high pressure, the addition of oxygen or high temperatures. Leaching may also be carried out with electricity. From the leaching solution the desired metal or its compound is recovered by precipitation or reduction using different methods. Reduction is carried out, for example, in cobalt and nickel production with gas. Electrolysis of metals in aqueous solutions is also considered to be a hydrometallurgical process. In the process of electrolysis the metallic ion is reduced to the metal. The metal is in a weak acid solution from which it precipitates on cathodes under the influence of an electrical current. Most non-ferrous metals can also be refined by electrolysis. Often metallurgical processes are a combination of pyro- and hydrometallurgical processes, depending on the ore concentrate to be treated and the type of metal to be refined. An example is nickel production.

Hazards and Their Prevention
Prevention of health risks and accidents in the metallurgical industry is primarily an educational and technical question. Medical examinations are secondary and have only a complementary role in the prevention of health risks. A harmonious exchange of information and collaboration between the planning, line, safety and occupational health departments within the company give the most efficient result in the prevention of health risks. The best and least costly preventive measures are those taken at the planning stage of a new plant or process. In planning of new production facilities, the following aspects should be taken into account as a minimum: · The potential sources of air contaminants should be enclosed and isolated. · The design and placement of the process equipment should allow easy access for maintenance purposes. · Areas in which a sudden and unexpected hazard may occur should be monitored continuously. Adequate warning notices should be included. For example, areas in which arsine or hydrogen cyanide exposure might be possible should be under continuous monitoring.

falls of heavy objects. Heat Heat stress illnesses such as heat stroke are a common hazard. training should be done whenever a new process is introduced.. The following are some of the specific hazards and precautions that are found in smelting and refining. gas explosions and explosions from contact of molten metal with water. Regular fixed monitoring of gases. work gloves and protective clothing). housekeeping and equipment maintenance. poor personal hygiene by eating and smoking in the worksite may considerably increase personal exposure. collisions with moving locomotives. traffic rules for moving equipment (including defined routes and an effective signal and warning system). appropriate personal protective equipment (PPE) (e. falls from a height (e. good storage. while accessing a crane cab). · Personal occupational hygiene sampling devices should be used in order to evaluate the real exposure of the individual worker. Injuries The smelting and refining industry has a higher rate of injuries than most other industries.· Addition and handling of poisonous process chemicals should be planned so that manual handling can be avoided. and slipping and tripping injuries from obstruction of floors and passageways. For example. safety shoes. · There should be a continuous system of training and education for safety and health personnel. New workers in particular should be thoroughly informed about potential health risks and how to prevent them in their own working environments. hard hats. travelling cranes and other mobile equipment. and a fall protection programme. · The management should have a health and safety monitoring system which produces adequate data for technical and economic decision making. as well as for foremen and workers. wagons. primarily due to infrared radiation from furnaces and molten metal. In addition. This is especially a problem when strenuous work must be done in hot environments. Precautions include: adequate training. · Work practices are important. the requirements of future changes or extensions of the process should be taken into account so that the occupational hygiene standards of the plant will not worsen. dusts and noise gives an overview of exposure but has only a complementary role in the evaluation of exposure dose. · In space planning. whenever possible..g. Sources of these injuries include: splattering and spills of molten metal and slag resulting in burns. .g.

reduced handling of materials and other process changes. spot cooling. Proper goggles and face shields should be worn. metal fumes can be a major problem. . heat-protective clothing and air-cooled suits. and mercury and cyanide exposures during gold refining. A hearing conservation program including audiometric testing and training should be instituted. clothing and tools. arsenic and cadmium). Where these are not adequate. Examples include nickel carbonyl in nickel refining. wetting down of materials. work breaks in cool areas and an adequate supply of beverages for frequent drinking. The smelting and refining of some metals can have special hazards. allowing sufficient time for acclimatization. arsenic in copper and lead smelting and refining. During smelting operations. If the source of the noise cannot be enclosed or isolated.Prevention of heat illnesses can involve water screens or air curtains in front of furnaces. Sulphuric acid is produced as a by-product of smelting operations and is used in electrolytic refining and leaching of metals. Electrical hazards can occur during electrolytic processes. Many smelting operations involve the production of large amounts of sulphur dioxide from sulphide ores and carbon monoxide from combustion processes.. High noise levels from crushing and grinding ore. insulated gloves. gases and other chemicals can occur during smelting and refining operations. enclosed air-conditioned booths. fluorides in aluminium smelting. respiratory protection would be needed. Precautions include proper electrical maintenance with lockout/tagout procedures. Dilution and local exhaust ventilation (LEV) are essential. containing lead. Other hazards Glare and infrared radiation from furnaces and molten metal can cause eye damage including cataracts. Skin and eye protection and LEV is needed. There can also be dust exposures during furnace maintenance operations. Crushing and grinding ore in particular can result in high exposures to silica and toxic metal dusts (e. Exposure can occur both to the liquid and to sulphuric acid mists. then hearing protectors should be worn. and ground fault circuit interrupters where needed. local and dilution exhaust ventilation. These processes require their own special precautions. High levels of infrared radiation may also cause skin burns unless protective clothing is worn. gas discharge blowers and high-power electric furnaces can cause hearing loss.g. fumes. automation of processes. Dust and fume emissions can be controlled by enclosure. Chemical hazards Exposure to a wide variety of hazardous dusts.

Pollution and Environmental Protection Emissions of irritant and corrosive gases like sulphur dioxide.Manual lifting and handling of materials can cause back and upper extremity injuries. The tolerance of vegetation to sulphur dioxide varies depending on the type of forest and soil. Tailings from the flotation process are pumped as slurry into sedimentation ponds.. silica and other pollutants. to meet emission standards. sedimentation ponds). Most of this water is recycled back into the process. Mechanical lifting aids and proper training in lifting methods can reduce this problem. Sulphur dioxide. iron sulphides. Wastewater effluent may contain a variety of toxic metals. one of the major contaminants. arsenic. COPPER. LEAD AND ZINC SMELTING AND REFINING* *Adapted from EPA 1995. blowdown slurries from sulphur dioxide conversion to sulphuric acid and sludges from surface impoundments (e. Large amounts of water are used in flotation processes such as copper concentration. sulphur dioxide and other hazardous gaseous wastes are controlled by scrubbing. . lead.g. In general. is recovered as sulphuric acid when present in sufficient quantity. Some slags can be reconcentrated and returned to smelters for reprocessing or recovery of other metals present. Solid-phase wastes include slags from smelting. the temperature at which it leaves the process. Particulate emissions are commonly controlled by fabric filters and electrostatic precipitators. Many of these solid-phase wastes are hazardous wastes that must be stored according to environmental regulations. Smelter management should include evaluation and control of emissions from the plant. Water is recycled in the process. to keep meteorological records and to be prepared to reduce output when weather conditions are unfavourable for dispersal of stack effluents. hydrogen sulphide and hydrogen chloride may contribute to air pollution and cause corrosion of metals and concrete within the plant and in the surrounding environment. fluorides. other materials in the gas stream and other factors must all be considered when planning measures to control air pollution. It is also desirable to maintain a weather station. Particulate emissions may contain non-specific particulates. Otherwise. Field trips are necessary to observe the effect of air pollution on residential and farming areas. The physical state of the material. This is specialized work which should be carried out only by personnel thoroughly familiar with the chemical properties and toxicities of the materials discharged from the plant processes. evergreen trees tolerate lower concentrations of sulphur dioxide than deciduous ones. cadmium and many other toxic metals. sulphuric acid and other impurities. Metal-containing process water and rainwater are cleaned in water-treatment plants before discharging or recycling. lead. Solid wastes can be contaminated with arsenic.

Copper
Copper is mined in both open pits and underground mines, depending upon the ore grade and the nature of the ore deposit. Copper ore typically contains less that 1% copper in the form of sulphide minerals. Once the ore is delivered above the ground, it is crushed and ground to a powdery fineness and then concentrated for further processing. In the concentration process, ground ore is slurried with water, chemical reagents are added and air is blown through the slurry. The air bubbles attach themselves to the copper minerals and are then skimmed off the top of the flotation cells. The concentrate contains between 20 and 30% copper. The tailings, or gangue minerals, from the ore fall to the bottom of the cells and are removed, dewatered by thickeners and transported as a slurry to a tailings pond for disposal. All water used in this operation, from dewatering thickeners and the tailings pond, is recovered and recycled back into the process. Copper can be produced either pyrometallurgically or hydrometallurgically depending upon the ore-type used as a charge. The ore concentrates, which contain copper sulphide and iron sulphide minerals, are treated by pyrometallurgical processes to yield high purity copper products. Oxide ores, which contain copper oxide minerals that may occur in other parts of the mine, together with other oxidized waste materials, are treated by hydrometallurgical processes to yield high purity copper products. Copper conversion from the ore to metal is accomplished by smelting. During smelting the concentrates are dried and fed into one of several different types of furnaces. There the sulphide minerals are partially oxidized and melted to yield a layer of matte, a mixed copper-iron sulphide and slag, an upper layer of waste. The matte is further processed by converting. The slag is tapped from the furnace and stored or discarded in slag piles onsite. A small amount of slag is sold for railroad ballast and for sand blasting grit. A third product of the smelting process is sulphur dioxide, a gas which is collected, purified and made into sulphuric acid for sale or for use in hydrometallurgical leaching operations. Following smelting, the copper matte is fed into a converter. During this process the copper matte is poured into a horizontal cylindrical vessel (approximately 10×4 m) fitted with a row of pipes. The pipes, known as tuyères, project into the cylinder and are used to introduce air into the converter. Lime and silica are added to the copper matte to react with the iron oxide produced in the process to form slag. Scrap copper may also be added to the converter. The furnace is rotated so that the tuyères are submerged, and air is blown into the molten matte causing the remainder of the iron sulphide to react with oxygen to form iron oxide and sulphur dioxide. Then the converter is rotated to pour off the iron silicate slag. Once all of the iron is removed, the converter is rotated back and given a second blow of air during which the remainder of the sulphur is oxidized and removed from the copper sulphide. The converter is then rotated to pour off the molten copper, which at this point is called blister copper (so named because if allowed to solidify at this point, it will have a bumpy surface due to the presence of gaseous oxygen and sulphur). Sulphur dioxide from the converters is collected

and fed into the gas purification system together with that from the smelting furnace and made into sulphuric acid. Due to its residual copper content, slag is recycled back to the smelting furnace. Blister copper, containing a minimum of 98.5% copper, is refined to high purity copper in two steps. The first step is fire refining, in which the molten blister copper is poured into a cylindrical furnace, similar in appearance to a converter, where first air and then natural gas or propane are blown through the melt to remove the last of the sulphur and any residual oxygen from the copper. The molten copper is then poured into a casting wheel to form anodes pure enough for electrorefining. In electrorefining, the copper anodes are loaded into electrolytic cells and interspaced with copper starting sheets, or cathodes, in a bath of copper sulphate solution. When a direct current is passed through the cell the copper is dissolved from the anode, transported through the electrolyte and re-deposited on the cathode starting sheets. When the cathodes have built-up to sufficient thickness they are removed from the electrolytic cell and a new set of starting sheets is put in their place. Solid impurities in the anodes fall to the bottom of the cell as a sludge where they are ultimately collected and processed for the recovery of precious metals such as gold and silver. This material is known as anode slime. The cathodes removed from the electrolytic cell are the primary product of the copper producer and contain 99.99+% copper. These may be sold to wire-rod mills as cathodes or processed further to a product called rod. In manufacturing rod, cathodes are melted in a shaft furnace and the molten copper is poured onto a casting wheel to form a bar suitable for rolling into a 3/8 inch diameter continuous rod. This rod product is shipped to wire mills where it is extruded into various sizes of copper wire. In the hydrometallurgical process, the oxidized ores and waste materials are leached with sulphuric acid from the smelting process. Leaching is performed in situ, or in specially prepared piles by distributing acid across the top and allowing it to percolate down through the material where it is collected. The ground under the leach pads is lined with an acid-proof, impermeable plastic material to prevent leach liquor from contaminating groundwater. Once the copper-rich solutions are collected they can be processed by either of two processes—the cementation process or the solvent extraction/electrowinning process (SXEW). In the cementation process (which is rarely used today), the copper in the acidic solution is deposited on the surface of scrap iron in exchange for the iron. When sufficient copper has been cemented out, the copper-rich iron is put into the smelter together with the ore concentrates for copper recovery via the pyrometallurgical route. In the SXEW process, the pregnant leach solution (PLS) is concentrated by solvent extraction, which extracts copper but not impurity metals (iron and other impurities). The copper-laden organic solution is then separated from the leachate in a settling tank. Sulphuric acid is added to the pregnant organic mixture, which strips the copper into an electrolytic solution. The leachate, containing the iron and other impurities, is returned to the leaching operation where its acid is used for further leaching. The copper-rich strip solution is passed into an electrolytic cell known as an electrowinning cell. An electrowinning cell differs from an electrorefining cell in that it

uses a permanent, insoluble anode. The copper in solution is then plated onto a starting sheet cathode in much the same manner as it is on the cathode in an electrorefining cell. The copperdepleted electrolyte is returned to the solvent extraction process where it is used to strip more copper from the organic solution. The cathodes produced from the electrowinning process are then sold or made into rods in the same manner as those produced from the electrorefining process. Electrowinning cells are used also for the preparation of starting sheets for both the electrorefining and electrowinning processes by plating the copper onto either stainless steel or titanium cathodes and then stripping off the plated copper. Hazards and their prevention The major hazards are exposure to ore dusts during ore processing and smelting, metal fumes (including copper, lead and arsenic) during smelting, sulphur dioxide and carbon monoxide during most smelting operations, noise from crushing and grinding operations and from furnaces, heat stress from the furnaces and sulphuric acid and electrical hazards during electrolytic processes. Precautions include: LEV for dusts during transfer operations; local exhaust and dilution ventilation for sulphur dioxide and carbon monoxide; a noise control and hearing protection programme; protective clothing and shields, rest breaks and fluids for heat stress; and LEV, PPE and electrical precautions for electrolytic processes. Respiratory protection is commonly worn to protect against dusts, fumes and sulphur dioxide. Table 82.1 lists environmental pollutants for various steps in copper smelting and refining. Table 82.1 Process materials inputs and pollution outputs for copper smelting and refining Process Copper concentration Material input Copper ore, water, chemical reagents, thickeners Copper concentrate, sulphuric acid Copper concentrate, siliceous flux Sulphur dioxide, particulate matter containing arsenic, antimony, cadmium, lead, mercury and zinc Sulphur dioxide, particulate matter containing arsenic, antimony, cadmium, lead, mercury and zinc Air emissions Process wastes Flotation wastewaters

Copper leaching Copper smelting

Uncontrolled leachate

Copper conversion

Copper matte, scrap copper, siliceous flux

Next. tin and copper oxide). During drossing. along with copper. The dross is removed and fed into a dross furnace for recovery of the non-lead useful metals. silver. In the sintering machine the lead feedstock is subjected to blasts of hot air which burn off the sulphur. During the fourth step. silica and lime is stored in piles and partially recycled.90 to 99. drossing and pyrometallurgical refining. zinc. smelting. the lead is refined by vacuum removal (distillation) of zinc. pyrite. A dross. These two materials combine with bismuth to form an insoluble compound that is skimmed from the kettle. The refined lead will have a purity of 99. coke. ―matte‖ (copper sulphide and other metal sulphides). arsenic. soda. Refining continues with the addition of calcium and magnesium. antimony and other elements. To enhance copper recovery. lowering the copper content to approximately 0. The lead oxide material existing after this process contains about 9% of its weight in carbon. Rough lead bullion from the blast furnace usually requires preliminary treatment in kettles before undergoing refining operations. limestone and other fluxing agents into a blast furnace for reducing. Other raw materials may be added including iron. caustic and particulates gathered from pollution control devices. and/or aluminium. The sinter is then fed along with coke. tin and arsenic are removed first. ash.g. creating sulphur dioxide. . various recycled and cleanup materials. blast furnace slag (primarily silicates). The lead is refined in a cast iron kettle by five stages. basically arsenic and antimony). Sulphur oxide emissions are generated in blast furnaces from small quantities of residual lead sulphide and lead sulphates in the sinter feed. The speiss and matte are sold to copper smelters for recovery of copper and precious metals. by weight). gold. and lead bullion (98% lead. To begin. which is composed of lead oxide.99% and may be mixed with other metals to form alloys or it may be directly cast into shapes. Then zinc is added and gold and silver are removed in the zinc slag. and metal oxides such as antimony. the lead bullion is refined using pyrometallurgical methods to remove any remaining non-lead saleable materials (e. bismuth. silica. sulphuric acid Lead The primary lead production process consists of four steps: sintering. a feedstock comprising mainly of lead concentrate in the form of lead sulphide is fed into a sintering machine.. floats to the top and solidifies above the molten lead. the bullion is agitated in a drossing kettle and cooled to just above its freezing point (370 to 425°C). Antimony. iron. The molten lead flows to the bottom of the furnace where four layers form: ―speiss‖ (the lightest material. In the final step caustic soda and/or nitrates may be added to the lead to remove any remaining traces of metal impurities. zinc.Electrolytic copper refining Blister copper. zinc.01%. limestone flux. where the carbon acts as a fuel and smelts or melts the lead material. The blast furnace slag which contains zinc. drossed lead bullion is treated by adding sulphur-bearing materials. All layers are then drained off.

fumes and sulphur dioxide. Table 82. Table 82. which may contain as little as 2% zinc. baghouse dust. a noise control and hearing protection programme. Four processing stages are generally used in hydrometallurgic zinc refining: calcining. soda ash. purification and electrowinning. pyrite. Roaster . noise from grinding and crushing operations and from furnaces. particulate Plant washdown matter contain-ing wastewater. zinc. metal fumes (including lead. slag cadmium and lead granulation water Process wastes Lead smelting Lead drossing Lead bullion. The latter accounts for approximately 80% of total zinc refining. sulphur. Precautions include: LEV for dusts during transfer operations. rest breaks and fluids for heat stress. sulphur dioxide and carbon monoxide during most smelting operations.Hazards and their prevention The major hazards are exposure to ore dusts during ore processing and smelting. and protective clothing and shields. particulate matter contain-ing cadmium and lead Sulphur dioxide. The zinc concentrate is then reduced to zinc metal in one of two ways: either pyrometallurgically by distillation (retorting in a furnace) or hydrometallurgically by electrowinning.2 lists environmental pollutants for various steps in lead smelting and refining. coke. limestone flux. Respiratory protection is commonly worn to protect against dusts. soda. iron. coke Air emissions Sulphur dioxide. from waste rock by crushing and flotation. is a high-temperature process (700 to 1000 °C) that converts zinc sulphide concentrate to an impure zinc oxide called calcine. Biological monitoring for lead is essential. or roasting. arsenic and antimony) during smelting. Calcining. silica.2 Process materials inputs and pollution outputs for lead smelting and refining Process Lead sintering Material input Lead ore. a process normally performed at the mining site. baghouse dust Lead sinter. caustic. local exhaust and dilution ventilation for sulphur dioxide and carbon monoxide. ash. coke Lead drossing bullion Lead refining Zinc Zinc concentrate is produced by separating the ore. leaching. and heat stress from the furnaces.

metal fumes (including zinc and lead) during refining and roasting. The elements recovered during purification include copper as a cake and cadmium as a metal. each cell is shut down. All of the calcining processes generate sulphur dioxide. suspension or fluidized-bed. Every 24 to 48 hours. Electrolytic processing of desulphurized calcine consists of three basic steps: leaching. noise from crushing and grinding operations and from furnaces. After leaching. This process charges the suspended zinc and forces it to deposit onto an aluminium cathode which is immersed in the solution. which increases the temperature of the electrolyte. purification and electrolysis. The calcine is then leached a second time in a stronger solution which dissolves the zinc. This second leaching step is actually the beginning of the third step of purification because many of the iron impurities drop out of the solution as well as the zinc. Leaching refers to the dissolving of the captured calcine in a solution of sulphuric acid to form a zinc sulphate solution. The zinc concentrate is then melted and cast into ingots and is often as high as 99. In general. Zinc electrowinning takes place in an electrolytic cell and involves running an electric current from a lead-silver alloy anode through the aqueous zinc solution. The process takes place at temperatures ranging from 40 to 85°C and pressures ranging from atmospheric to 2.4 atmospheres. Purification is usually conducted in large agitation tanks. The calcine may be leached once or twice. During electrowinning a portion of the electrolyte passes through cooling towers to decrease its temperature and to evaporate the water it collects during the process. Electrolytic zinc smelters contain as many as several hundred cells. Hazards and their prevention The major hazards are exposure to ore dusts during ore processing and smelting. the solution is purified in two or more stages by adding zinc dust. and the zinc mechanically stripped from the aluminium plates. After purification the solution is ready for the final step. In the double-leach method.types include multiple-hearth. which is controlled and converted to sulphuric acid as a marketable process by-product. Electrolytic cells operate at temperature ranges from 30 to 35°C at atmospheric pressure. heat stress from the furnaces and sulphuric acid and electrical hazards during electrolytic processes. electrowinning. or roasted. the calcine is dissolved in a slightly acidic solution to remove the sulphates. This mixture is then heated. the zinc-coated cathodes removed and rinsed. . to vaporize the zinc oxide which is then moved out of the reaction chamber with the resulting gas stream. The gas stream is directed to the baghouse (filter) area where the zinc oxide is captured in baghouse dust. A portion of the electrical energy is converted into heat.995% pure. sulphur dioxide and carbon monoxide during most smelting operations. The solution is purified as the dust forces deleterious elements to precipitate so that they can be filtered out. calcining begins with the mixing of zinc-containing materials with coal.

Dinman Process Overview Bauxite is extracted by open-pit mining. sulphuric acid. Table 82. The production of the metal comprises two basic steps: 1. 2. fumes and sulphur dioxide. spent electrolyte Zinc-acid solution. . local exhaust and dilution ventilation for sulphur dioxide and carbon monoxide. iron Dilute sulphuric acid Process wastes Zinc leaching Zinc calcine. barium carbonate or strontium. Table 82. PPE. Respiratory protection is commonly worn to protect against dusts. rest breaks and fluids for heat stress. Reduction of alumina to virgin aluminium metal employing the Hall-Heroult electrolytic process using carbon electrodes and cryolite flux. Reduction. The richer ores are used as mined. zinc dust Zinc in a sulphuric acid/aqueous solution. a noise control and hearing protection programme. The lower grade ores may be beneficiated by crushing and washing to remove clay and silica waste. and LEV. The resulting hydrate is crystallized and calcined to the oxide in a kiln or fluid bed calciner. limestone. Refining.3 Process materials inputs and pollution outputs for zinc smelting and refining Process Zinc calcining Material input Zinc ore.Precautions include: LEV for dusts during transfer operations. lead-silver alloy anodes. aluminium cathodes. Production of alumina from bauxite by the Bayer process in which bauxite is digested at high temperature and pressure in a strong solution of caustic soda. protective clothing and shields. and electrical precautions for electrolytic processes. particulate matter containing zinc and lead Wastewaters containing sulphuric acid Wastewaters containing sulphuric acid.3 lists environmental pollutants for various steps in zinc smelting and refining. coke Air emissions Sulphur dioxide. colloidal additives Zinc purification Zinc electrowinning ALUMINIUM SMELTING AND REFINING Bertram D.

In such smelters exposure to polycyclic hydrocarbons normally occurs in the electrode manufacturing facilities. The so-called ―prebake‖ process utilizes electrodes manufactured as noted below. It should be noted that the pitch used to form such electrodes represents a distillate which is derived from coal or petroleum tar. In the conversion of this tar to pitch by heating. such pitch should not present the same hazards in its use as coal or petroleum tars since these classes of compounds ought not to be present. the final pitch product has boiled off essentially all of its low-boiling point inorganics. The anodes and cathodes are most frequently made from a mixture of ground petroleum-derived coke and pitch. SO2. In addition. in extracting these. Coke first is ground in ball mills. considerable amounts of coal tar pitch volatiles are evolved into the cell room environment. There are some indications that the carcinogenic potential of such pitch . Metal rods are inserted into the anodic mass as conductors for a direct current electric flow. To this exposure is added those pitch volatiles generated as the baking of the pitch-coke mass proceeds. Within the last decade the industry has tended to either not replace or to modify existent Soderberg type reduction facilities as a consequence of the demonstrated carcinogenic hazard they present. There are presently two major types of Hall-Heroult electrolytic cells in use. Indeed. this mixture bakes into a hard graphitic mass in situ. These anode or cathode blocks are next heated in a gas-fired furnace for several days until they form hard graphitic masses with essentially all volatiles having been driven off. the mixture of coke and pitch binder is put into hoppers whose lower ends are immersed in the molten cryolite-alumina bath mixture. Finally they are attached to anode rods or saw-grooved to receive the cathode bars. tasks are more commonly performed from enclosed mechanical cranes.Experimental development suggests that in the future aluminium may be reduced to the metal by direct reduction from the ore. Smelters utilizing the Soderberg-type cell do not require facilities for the manufacture of baked carbon anodes. Rather. Carbon electrode manufacture The electrodes required by pre-bake electrolytic reduction to pure metal are normally made by a facility associated with this type of aluminium smelting plant. the persistence of older. with the increasing automation of reduction cell operations— particularly the changing of anodes. e. especially during mixing mills and forming presses. as well as aliphatic compounds and one. this tendency will tend to become more aggravated in such older. unimproved operations. By contrast. especially as they age. Thus. As the mixture of pitch and coke is heated by the molten metal-cryolite bath within the cell. then conveyed and mixed mechanically with the pitch and finally cast into blocks in a moulding presses.g. in those economies wherein adequate capital investment is not readily available. manually operated reduction processes will continue to present the risks of those occupational disorders (see below) previously associated with aluminium reduction plants. Consequently worker exposures and the risk of developing those disorders associated with aluminium smelting are gradually decreasing in modern facilities.. These rods must be replaced periodically.and two ring aromatic compounds.

The potential hazards associated with the inhalation of excessive doses of aluminium oxide produced in this process are discussed below. All workers involved in the Bayer process should be well informed of the hazards associated with handling caustic soda. aprons. Descaling of tanks by pneumatic hammers is responsible for severe noise exposure. PPE (e.g. heat stress disorders.. Hazards and Their Prevention The hazards and preventive measures for aluminium smelting and refining processes are basically the same as those found in smelting and refining in general. However. As mechanized potroom work is remotely performed from enclosed cabins. these protective measures will become less necessary. the individual processes present certain specific hazards. the possibility of the presence of crystalline silica in bauxite ores should be considered. there is little convincing evidence that such an entity exists. gauntlets. should be provided with air-supplied respiratory protective equipment. goggles. In all sites at risk. efficient dust masks are necessary for protection against carbon dust. Workers with more severe dust and fume exposure. respirators. cryolite and hydrofluoric acid fumes. eyewash fountains and basins with running water and deluge showers should be provided. wool has proved to have a good resistance to these fumes. Electrolytic reduction Electrolytic reduction exposes workers to the potential for skin burns and accidents due to molten metal splashes. All workers handling molten metal should be supplied with visors. aprons and boots) should be supplied. with notices explaining their use. gloves. . dust and fumes. Electrolytic reduction cells may emit large quantities of dusts of fluoride and alumina. however. Mining Although sporadic references to ―bauxite lung‖ occur in the literature. noise. Bayer process The extensive use of caustic soda in the Bayer process presents frequent risks of chemical burns of the skin and eyes. electrical hazards. particularly in Soderberg operations. Respirators with charcoal cartridges or alumina-impregnated masks give adequate protection against pitch and fluorine fumes. the other for personal clothing) should be provided and all employees encouraged to wash thoroughly at the end of the shift. armlets and spats to protect them against burns.products may not be as great as the more complex mixture of tars and other volatiles associated with the incomplete combustion of coal. Showers and double locker accommodations (one locker for work clothing. Workers employed on the Gadeau low-temperature process should be supplied with special gloves and suits to protect them from hydrochloric acid fumes given off when the cells start up.

personnel should also be trained to give cardiopulmonary resuscitation to victims of electric shock accidents. gauntlets. since the heat of molten metal causes such heated fibers to melt and adhere to the skin. heated road tankers can be used to transport liquid pitch to the works where it is pumped automatically into heated pitch tanks). Finally. Moreover. variable degrees of mottling of permanent teeth have been reported if exposure occurred during the developmental phase of permanent teeth growth. in the event of extreme and protracted exposure to fluoride. further intensifying skin burns. Other Health Effects The hazards to workers. and extra protection can be provided by alginate-base barrier creams. Finally. The first stage of this condition consists of a simple increase in bone density. They and their supervisors should also be trained to recognise incipient heat-induced disorders in themselves and their co-workers. calcification of the ligaments of the pelvis is next seen. the general population and the environment resulting from the emission of fluoride-containing gases. All those working here should be trained to take the proper measure necessary to prevent the occurrence or progression of the heat disorders. Regular checks on atmospheric dust concentrations should be made with a suitable sampling device.4). The potential for molten metal splashes and severe burns are widespread at many sites in reduction plants and associated operations. exhaust ventilation equipment with bag filters should be installed. epitheliomata or dermatitis are also prudent. or where inadequate control of fluoride effluents continued. high-frequency noise.. calcification of the paraspinal and other . enclosure of pitch and carbon grinding equipment further effectively minimizes exposures to heated pitches and carbon dusts. and these should be followed up by clinical examinations when necessary. variable degrees of bony fluorosis have been seen. workers should undergo regular audiometric examination to detect hearing loss.. Regular skin examinations to detect erythema. aprons.In carbon-electrode manufacturing shops. Among smelter workers prior to 1950. In order to reduce the risk of handling pitch. As fluoride is further absorbed into bone. transport of this material should be mechanized as far as possible (e. In children living in the vicinity of poorly controlled aluminium smelters. smokes and dusts due to the use of cryolite flux have been widely reported (see table 82. Workers doing hot work should be instructed prior to the onset of hot weather to increase fluid intake and heavily salt their food. In addition to protective clothing (e. Periodic x-ray examinations should be carried out on workers exposed to dust. spats and face visors) the wearing of synthetic apparel should be prohibited. Workers exposed to high noise levels should be supplied with hearing protection equipment such as earplugs which allow the passage of low-frequency noise (to allow perception of orders) but reduce the transmission of intense.g.g. Individuals using cardiac pacemakers should be excluded from reduction operations because of the risk of magnetic field induced dysrhythmias. particularly marked in the vertebral bodies and pelvis.

. is characterized by variable airflow resistance. sulphur dioxide. such advanced stages have rarely if ever been seen in aluminium smelter workers. While the occurrence of this condition has been correlated with potroom concentrations of fluoride. particulate and gaseous fluorides. Finally. Given the complex mixture of dusts and fumes (e. sand and caustic Alumina clarification and precipitation Alumina calcination Primary electrolytic aluminium smelting Since the early 1980s an asthma-like condition has been definitively demonstrated among workers in aluminium reduction potrooms. Table 82. depending upon the intensity and character of the exposure. caustic/water vapour Alumina slurry. The condition usually is ameliorated with removal from the workplace following vacations and so on. Its clinical symptoms consist of wheezing. mechanization of potroom operations should minimize if not totally eliminate any fluoride associated hazards. plus low concentrations of the oxides of vanadium. carbon anodes. While this last stage has been seen in its severe form in cryolite processing plants. starch. or both. referred to as occupational asthma associated with aluminium smelting (OAAAS). By proper work practices and adequate ventilatory control. despite 25 to 40 years of such work. ranging from 1 week to 10 years. C2F6 . and is not precipitated by stimuli outside the workplace. workers in such reduction operations can be readily prevented from developing any of the foregoing x-ray changes. Apparently the less severe x-ray changes in bony and ligamentous structures are not associated with alterations of the architectural or metabolic function of bone. cryolite Particulates and water vapour Fluoride—both gaseous and particulates. nickel and . sodium hydroxide Particulates. water Aluminium hydrate Alumina. The latent period between commencement of work exposure and the onset of OAAAS is highly variable.CF4 and perfluorinated carbons (PFC) Wastewater containing starch. carbon monoxide.g.ligamentous structures as well as joints are noted. bronchial hyperresponsiveness. carbon dioxide. electrolytic cells. sulphur dioxide. but will become more frequent and severe with continued work exposures. chest tightness and breathlessness and non-productive cough which are usually delayed some several hours following work exposures. it is not clear that the aetiology of the disorder arises specifically from exposure to this chemical agent. This aberration.4 Process materials inputs and pollution outputs for aluminium smelting and refining Process Bauxite refining Material input Air emissions Process wastes Bauxite.

chromium) it is more likely that such fluorides measurements represent a surrogate for this complex mixture of fumes. this diagnosis is unlikely. the excess cancer risk is less wellestablished. Exposure to the polycyclic aromatics associated with breathing of pitch fume and particulates have been demonstrated to place Soderberg-type reduction cell personnel in particular at an excessive risk of developing urinary bladder cancer. or true occupational asthma. Because of the occasional need to expend in excess of 300 kcal/h in the course of changing anodes or performing other strenuous work in the presence of molten cryolite and aluminium.g. the reactive airway dysfunction syndrome (RADS). The causal process which results in this disorder is determined with difficulty in an individual case. non-specific bronchial hyperresponsiveness. or in its absence. (However. this phenomenon can eventually disappear after the disorder subsides with removal from work exposures. the presence of variable airflow limitation. after electrodes have been baked for several days at about 1. requiring a compatible history. However. Heat stroke has occurred but rarely among aluminium smelter workers except among those with known predisposing health alterations (e. alcoholism. Workers inadequately heat acclimatized or physically conditioned. much of the literature regarding neurological effects in such workers derives from the presumption that aluminium absorption results in human neurotoxicity. until such associations are more reproducibly demonstrable. It has been clearly shown that aluminium is absorbed via the lungs and excreted in the urine at levels greater than normal. the absence of atopy cannot predict whether this condition will occur subsequent to work exposures. particularly in reduction cell room workers. affected individuals most usually need be removed from continued work exposures. humid conditions of summer. production of pharmacologically induced bronchial hyperresponsivity. polycyclic aromatic compounds are practically totally combusted or .) Since this disorder tends to become progressively more severe with continued exposure. Diagnosis of this condition is presently problematic. However. While individuals with pre-existent atopic asthma should initially be restricted from aluminium reduction cell rooms. whose salt intake is inadequate or who have intercurrent or recent illness are particularly prone to development of heat exhaustion and/or heat cramps while performing such arduous tasks.. In addition. There are presently reports suggesting that aluminium may be associated with neurotoxicity among workers engaged in smelting and welding this metal. Signs and symptoms of OAAAS may result from: preexisting allergy-based asthma. Such episodes are most likely to occur when the weather initially changes from the moderate to hot. heat disorders may be seen during periods of hot weather. But if the latter is not demonstrable. Accordingly.200 °C. gases and particulates found in potrooms. Workers in carbon electrode plants where mixtures of heated coke and tar are heated are assumed to also be at such risk. the connection between aluminium and occupational neurotoxicity must be considered speculative at this time. ageing). work practices which result in accelerated anode changing or employment over two successive work shifts during hot weather will also predispose workers to such heat disorders. It presently appears that this condition is one of an increasingly important group of occupational diseases: occupational asthma.

at present such evidence is fragmentary and inconsistent. severe electrical shock accidents may occur particularly as the electrical supply is an alternating. high voltage current. Exposure to ultra-low frequency electromagnetic fields also occur in reduction plants. Cases of localized skin tumours have occurred among carbon electrode workers where inadequate personal hygiene was practised. tentative threshold limit values for static magnetic fields. in the power house at the point where the high-voltage supply joins the series-connection network of the potroom. there have been occasional reports that carbon electrode makers may develop simple pneumoconiosis with focal emphysema. However. Because health concerns have been raised regarding exposures associated with electromagnetic power fields. The electrolytic reduction cells are run in series from a low-voltage high-amperage current supply and. Hence the reduction cells utilizing prebaked electrodes have not been as clearly shown to present an undue risk of development of these malignant disorders. either experimentally or clinically. sub-radio frequency and static electric fields.g.g. During electrode manufacture. accordingly. the electromagnetic fields generated in the potrooms are mainly of the static or standing field type. ―potroom asthma‖) which are described elsewhere in this Encyclopaedia. It must be recognized that the power supplied to electrolytic reduction cells is direct current. Where such dust exposures have been severe and inadequately controlled. The grinding of coke in ball mills produces noise levels of up to 100 dBA. coherent or reproducible epidemiological evidence of adverse health effects due to electromagnetic fields in aluminium reduction plants have not been convincingly demonstrated. in contrast to low frequency electromagnetic fields.volatilized and are no longer associated with such anodes or cathodes. Finally. well below present standards. Other neoplasia (e. especially at the far-ends of these rooms adjacent to rectifier rooms.. Both the simple and complicated pneumoconioses are indistinguishable from the corresponding condition of coalworkers’ pneumoconiosis. Editor’s note: The aluminium production industry has been classified as a Group 1 known cause of human cancers by the International Agency for Research on Cancer (IARC). A variety of exposures have been associated with other diseases (e. cases of electric shock are not usually severe. the flux levels found in the nearby potrooms are minimal. exposure to sunlight induces photosensitization with increased irritation.. However. Electrode manufacture Workers in contact with pitch fumes may develop erythema. after excision and change of job no further spread or recurrence is usually noted. the use of pneumatic crust breakers in the potrooms produce noise levels of the order of 100 dBA. . the flux levels of the magnetic fields measured in present day cell rooms are commonly found to be within presently proposed. the exposure of workers in this industry has been brought into question. Such fields. are even less readily shown to exert consistent or reproducible biological effects. In addition. considerable quantities of carbon and pitch dust can be generated. non-granulocytic leukaemia and brain cancers) have been suggested to occur in aluminium reduction operations. consequently. In the vicinity of the electrolytic cells. complicated by the development of massive fibrotic lesions.

elevator dredges are used. the gold is separated outside the crushing apparatus. from solid to liquid. The process of amalgamation is based on the ability of gold to alloy with metallic mercury to form amalgams of varying consistencies. The gold extraction process consists of feeding finely ground ore into a leaching tub and filtering a solution of potassium or sodium cyanide through it. This crumbles the material and washes it away through special sluices in which the gold settles. leaving behind the solid gold. The gold-bearing sand sinks through perforations in the trommel and drops onto shaking tables for further concentration. consisting of flat-bottomed boats which use a chain of small buckets to scoop up material from the river bottom and empty it into a screening container (trommel). in the United States). the gold is recovered from the gold cyanide solution by adding aluminium or zinc dust. fresh mercury is added. The lighter sand and gravel are gradually washed off. which involves filling a circular dish with goldbearing sand or gravel. These are the processes of amalgamation and cyanidation. Ryzik* *Adapted from the 3rd edition. More advanced hydraulic gold mining consists of directing a powerful stream of water against the gold-bearing gravel or sand.g. In a separate operation. known as sands. Then the remaining mercury is pressed out of the amalgam. There are two main methods for the extraction of gold from ore. The silt is separated from the gold cyanide solutions by adding thickeners and by vacuum filtration. The purified and washed amalgam is then pressed. while the lighter gravel is floated off. The amalgamation process is rare today. Encyclopaedia of Occupational Health and Safety. Before the amalgam is removed. The gold can be fairly easily removed from the amalgam by distilling off the mercury. and smaller amorphous particles. The amalgam removed from the apparatus is washed free of any admixtures by water in special bowls. For river mining.A. because of environmental concerns. The simplest method of gold mining is panning. especially with low grade ores and mine tailings.. Gadaskina and L. in which the cyanide solution is poured over a levelled heap of coarsely crushed ore. in China and Brazil) and on a large scale in underground mines (e. In both instances. leaving the gold particles near the centre of the pan. The material is rotated in the trommel as water is directed on it. Extraction of gold by means of cyanidation is based on the ability of gold to form a stable watersoluble double salt KAu(CN)2 when combined with potassium cyanide in association with oxygen.g. In both processes the mercury is removed from the amalgam by distillation. in amalgamators or sluices (an inclined table covered with copper sheets). Heap leaching.. known as silt. In internal amalgamation. except in small scale mining. is becoming more popular. . being heavier. In external amalgamation.g.D. The sand. in South Africa) and in open pit mining (e. The pulp resulting from the crushing of gold ore consists of larger crystalline particles. Gold mining is carried out on a small scale by individual prospectors (e. is deposited at the bottom of the apparatus and allows solutions (including silt) to pass through. the gold is separated inside the crushing apparatus at the same time as the ore is crushed. concentrated acid is added in a digest reactor to dissolve the zinc or aluminium.. holding it under a stream of water and swirling it.GOLD SMELTING AND REFINING I.

The charcoal can be reactivated by roasting. workers must be provided with the PPE necessary for work with mercury. lead and zinc smelting and refining‖ in this chapter). Both amalgamation and cyanidation produce metal that contains a considerable quantity of impurities. These ventilation systems must be particularly efficient in premises where mercury is distilled off. all surfaces must be regularly cleaned so as to remove all mercury deposits. In order to prevent this. The gold is then recovered by electrolysis. and the cyanide can be recovered and reused. as well as the acids present in the ore. Stocks of mercury must be kept in hermetically sealed metal containers under a special exhaust hood. unless it is further electrolytically refined in order to produce a degree of fineness of up to 999. the pure gold content rarely exceeding 900 per mil fineness. In amalgamation processes the mercury must be placed on the sluices and the amalgam removed in such a manner as to ensure that the mercury does not come in contact with the skin of the hands (by using shovels with long handles. All premises intended for operations involving the use of mercury must be equipped with general and local exhaust ventilation. the processing of amalgam and the distilling off of mercury must be carried out in separate isolated premises in which the walls. protective clothing impervious to mercury and so on).8 per mil and more. with no possibility of the hands being touched by mercury. mercury poisoning has been reported amongst amalgamation and distilling workers. lead and other metals (see the article ―Copper. This necessitates measures to prevent the formation and spread of dust in mine workings. Hydrogen cyanide is also produced when the acid is added to dissolve the aluminium or zinc. The risk of mercury exposure in amalgamation has become a serious problem in several countries in the Far East and South America. floors. Gold is also recovered as a by-product from the smelting of copper. and the air must be monitored . water and air. and the gold extracted using concentrated alkaline cyanide in alcoholic solution. apparatus and work surfaces are covered with material which will not absorb mercury or its vapours. ceilings.Under the influence of carbonic acid. the cyanide solutions decompose and give off hydrogen cyanide gas. The processing of the amalgam and the removal or pressing of mercury must also be as fully mechanized as possible. The gold-containing charcoal is removed by screening. alkali is added (lime or caustic soda). The separation of gold from arsenical ores gives rise to arsenic exposure of mine workers and to pollution of air and soil with arsenic-containing dust. In the mercury extraction of gold. Another cyanidation technique involves the use of activated charcoal to remove the gold. Hazards and Their Prevention Gold ore occurring in great depths is extracted by underground mining. when the amalgam is purified or pressed and when the mercury is distilled off. workers may be exposed to high airborne mercury concentrations when mercury is placed in or removed from the sluices. Thickeners are added to the gold cyanide solution before slurrying with activated charcoal in order to keep the charcoal in suspension.

Contamination of the air by hydrogen cyanide in cyanidation plants is dependent on air temperature. eczema and pyoderma (an acute inflammatory skin disease with pus formation). Cyanide contamination of wastewater is also a great concern. floors. the volume of material being processed. Emissions of hydrogen cyanide gas. are treated with a scrubber before being exhausted out the stack. there can be substantial contamination by cyanide dust and hydrogen cyanide gas. in addition to a high frequency of allergic dermatitis. in addition. If the opening of drums containing cyanide salts and the feeding of these salts into dissolving tubs is not mechanized. In a contaminated area of Venezuela. cyanidation apparatus must be hermetically sealed and equipped with LEV backed up by adequate general ventilation and leak monitoring. In gold cyanidation plants. open areas and stairs of the premises must be covered with non-porous materials and regularly cleaned with weak alkaline solutions. . Smoking should be prohibited and workers should be provided with separate facilities for eating and drinking. All cyanidation apparatus and the walls. The high level of mercury in the surface soil and rubber sediments of the contaminated area constitutes a serious occupational and public health risk. The use of acids to break down zinc in the processing of gold slime may give off hydrogen cyanide and arsine. Environmental Effects There is evidence of exposure to metallic mercury vapour and methylation of mercury in nature. with the use of local exhaust hoods. ventilation. Proper organization of the preparation of cyanide solutions is particularly important. Cyanide solutions should be fed in through closed systems by automatic proportioning pumps. Cyanide solutions should be treated before being released or should be recovered and reused.systematically in premises used for amalgamation and distilling. These operations must therefore be performed in specially equipped and separated premises. There should also be medical monitoring. particularly where the gold is processed. gold prospectors have been using mercury to separate gold from auriferous sand and rock powders for many years. First-aid equipment should be available and should contain material for immediately removing any cyanide solution that comes in contact with workers’ bodies and antidotes for cyanide poisoning. Workers must be supplied with personal protective clothing impervious to cyanide compounds. the correct degree of alkalinity must be maintained in all cyanidation apparatus. the concentration of the cyanide solutions in use. settlements and fish from gold mining areas of Brazil. in the digest reactor. the quality of the reagents and the number of open installations. the mercury concentrations in edible parts of locally consumed fish surpassed by almost 6 times the Brazilian advisory level for human consumption (Palheta and Taylor 1995). Medical examination of workers in gold-extracting factories has revealed symptoms of chronic hydrogen cyanide poisoning. In one study of water. for example.

Foundry work comprises: · making a pattern of the desired article · making the mould and cores and assembling the mould · melting and refining the metal · pouring the metal into the mould · cooling the metal casting · removing the mould and core from the metal casting · removing extra metal from the finished casting. the merchant blast furnace may turn all its output . especially aluminium foundry and die-cast operations. steel. The most prominent foundry process is sand moulding of iron. Wooden patterns have been replaced by metal and plastic. remains important from an occupational health perspective. The mould may contain a core to determine the dimensions of any internal cavity in the final casting. Mirer Founding. and a wide range of alloys are used. nickel and magnesium. both free standing and those producing for the plumbing equipment industry. The different additives have little impact on workplace exposures.FOUNDRIES Franklin E. Although the metal founding industry may be assumed to start by remelting solid material in the form of metal ingots or pigs. The major customers of the largest ferrous foundries are the auto. cerium or other additives (often called ladle additives) to the ladles of molten metal before pouring to make nodular or malleable iron castings. and as aluminium is substituted for cast iron. brass and bronze are traditional cast metals. Non-ferrous foundries. Iron foundry employment has decreased as engine blocks become smaller and can be poured in a single mould. For instance. The largest sector of the foundry industry produces grey and ductile iron castings. are used in foundry products. Ductile iron foundries add magnesium. construction and agricultural implement industries. or metal casting. have heavy employment. Brass foundries. new substances have been developed for producing cores and moulds. In recent years. Iron. chromium. Steel and malleable iron make up the balance of the ferrous foundry industrial sector. the iron and steel industry in the large units may be so integrated that the division is less obvious. are a shrinking sector which. processes have become more mechanized and automatic. titanium. however. involves the pouring of molten metal into the hollow inside of a heatresistant mould which is the outside or negative shape of the pattern of the desired metal object. The basic principles of foundry technology have changed little in thousands of years. Gray iron foundries use iron or pig iron (new ingots) to make standard iron castings. cadmium and thorium. and even more toxic metals such as beryllium. However.

using moulds of iron or steel. limestone and metal. heat treatment or painting before the finished article will meet the specifications of the buyer. There is in fact a separate section of the steel trade known for this reason as ingot moulding. stripping or knockout) and the casting is cleaned and dressed (despruing. shot-blasting or hydro-blasting and other abrasive techniques). Special hazards include carbon monoxide and heat. and investment casting. Electric arc furnace The furnace is charged with ingots. In general. Moulds made from silica sand bound with clay predominate in the iron foundry sector. Sand casting is the most widely used method. the remelting of pig iron is also a refining process. electric arc. Process Overview On the basis of the designer’s drawings. open at the top with hinged doors at the bottom.into pig iron. the mould and core material are removed (shakeout. a corebox is made that will produce suitable cores to dictate the internal configuration of the final article. a pattern conforming to the external shape of the finished metal casting is constructed. In the normal iron foundry. In the same way.000 kgf/cm2.5 Types of foundry furnaces Furnace Cupola furnace Description A cupola furnace is a tall. channel or coreless induction type (see table 82. When the metal has cooled. Cores traditionally produced by baking silica sand bound with vegetable oils or natural sugars have been substantially replaced. the molten metal is removed at the bottom. often a light alloy. but in an integrated plant some iron may be used to produce castings. where the same thing can occur. Molten metal is poured into the assembled mould either via a ladle or directly from the furnace. In the non-ferrous foundries the process of melting may require the addition of metals and other substances. These include: permanent mould casting. Modern founding technology has developed new techniques to produce moulds and cores. and the blast furnace iron may be taken molten to be turned into steel. Table 82. thus taking part in the foundry process.5). is forced into a metal mould under pressures of 70 to 7. It is charged from the top with alternate layers of coke. but other techniques are available. size of casting and degree of mechanization. the health and safety hazards of foundries can be classified by type of metal cast. The ―lost foam‖ process uses polystyrene foam patterns in sand to make aluminium castings. moulding process. crucible. where a wax pattern is made of each casting to be produced and is covered with refractory which will form the mould into which the metal is poured. scrap. rotary. Relevant metallurgical or chemical analyses are performed. Metals or alloys are melted and prepared in a furnace which may be of the cupola. die casting. and thus constitutes an alloying process. vertical furnace. Certain castings may require welding. alloy metals and fluxing . in which the molten metal. reverberatory.

Both the fireplace and metal charge are covered by an arched roof. for example. the airborne dust burden may be even higher than in the conventional foundry. This horizontal furnace consists of a fireplace at one end. A long. The flame in its path from the fireplace to the stack is reflected downwards or reverberated on the metal beneath. A type of induction furnace. However. the machine usually has built-in dust control devices. Special hazards include metal fumes. A review of air sampling data in the middle 1970s showed higher dust levels in large American production foundries than in small foundries sampled during the same period. Hazards may also be specific to a particular foundry process. Special hazards include metal fumes and noise. melting it. Conveying by pneumatic . Crucible furnace Rotary furnace Channel furnace Reverberatory furnace Hazards such as the danger arising from the presence of hot metal are common to most foundries. Installation of exhaust hoods over transfer points on belt conveyors. An arc is produced between three electrodes and the metal charge. should be normal practice. irrespective of the particular casting process employed. When ready. and transfer points and sand spillage may be sources of considerable quantities of airborne dust. The crucible or container holding the metal charge is heated by a gas or oil burner. and a stack or chimney at the other end. metal fumes. For example. combined with scrupulous housekeeping. When ready. inducing an electric current in the outer edge of the metal charge that heats the metal because of the high electrical resistance of the metal charge. by machine and castings are cleaned by shot blasting or hydroblasting. and the dust hazard is reduced. Melting progresses from the outside of the charge to the inside. to refine the metal and protect the furnace roof from excessive heat. which contain most of the typical foundry hazards. in view of the high production rates. When moulding is done. The mechanized or production foundry employs the same basic methods as the conventional iron foundry. the electrodes are raised and the furnace tilted to pour the molten metal into the receiving ladle. The metal is kept from contact with the solid fuel. A slag with fluxes covers the surface of the molten metal to prevent oxidation. separated from the metal charge by a low partition wall called the fire-bridge. the use of magnesium presents flare risks not encountered in other metal founding industries. noise and heat. Special hazards include carbon monoxide.agents. inclined rotating cylindrical furnace that is charged from the top and fired from the lower end. melting the metal. Induction furnace An induction furnace melts the metal by passing a high electric current through copper coils on the outside of the furnace. This article emphasizes iron foundries. sand is frequently moved from place to place on an open-belt conveyor. the crucible is lifted out of the furnace and tilted for pouring into moulds.

The crane cab should be well protected and the operators properly trained. shakeout. Sand is added to the system from core making. In many foundries. Sand is cycled from sand mix. open at the top with hinged doors at the bottom. cooling. moulding. Tidiness and efficient supervision of the stacks of raw materials are essential to minimize the risk of injury from slippages of heavy objects. iron moves from melting to pouring. . which starts with new sand. lined with refractory and charged with coke. scrap iron and limestone. the noise of metal-on-metal impact can be reduced by fitting rubber noisedampening liners to storage skips and bins. pattern-making 3. The charging platform is necessarily above ground level and can present a hazard unless it is level and has a non-slip surface and strong rails around it and any floor openings. casting cleaning. Cranes with large electromagnets or heavy weights are often used to reduce the scrap metal to manageable sizes for charging into the cupola and for filling the charging hoppers themselves. melts and purifies the iron. shakeout and back to sand mixing. shakeout/knockout 6. almost any of these processes may be carried out simultaneously or consecutively in the same workshop area. metal melting and pouring 2. moulding 4. an iron foundry can be presumed to comprise the following six sections: 1. coremaking 5. If the charging process is found to be too noisy.systems is sometimes economically possible and results in a virtually dust-free conveying system. Air is blown through the charge from openings (tuyers) at the bottom. Charge materials are fed into the top of the cupola by crane during operation and must be stored close at hand. vertical furnace. usually in compounds or bins in the yard adjacent to the charging machinery. In a typical production foundry. combustion of coke heats. Iron Foundries For simplicity. Melting and pouring The iron founding industry relies heavily on the cupola furnace for metal melting and refining. cleaning and shipping as a finished casting. Employees handling raw materials should wear hand leathers and protective boots. Careless charging can overfill the hopper and can cause dangerous spillage. The cupola is a tall.

To protect the workers from falling objects. safety harnesses. Selfcontained breathing apparatus and resuscitation equipment should be maintained in readiness.Cupolas generate large quantities of carbon monoxide. if working at a height. Procedures must be worked out in advance for tapping out iron and for shutting down when hot spots develop or if the water cooling system is disabled. Dropping the cupola bottom is a skilled and dangerous operation requiring trained supervision. When emergency work is carried out. Employees in metal and pouring sections of the foundry should be provided with hard hats. If a problem occurs. Visible white-hot metal is a danger to workers’ eyes due to the emission of infrared and ultraviolet radiation. Both continuous and spot monitoring of exposure levels are needed. a confinedspace entry system of contaminant monitoring should be developed and enforced. Goggles and protective clothing are essential. Delineation of a nonauthorized no-entry zone is a statutory requirement under the British Iron and Steel Foundries Regulations of 1953. These assignments should be considered confined-space entries and appropriate precautions taken. great caution must be exercised to avoid risks of burns to workers from the hot metal and slag. Workers tapping cupolas (transferring molten metal from the cupola well to a holding furnace or ladle) must observe rigorous personal protection measures. so that while one is being repaired the others operate. tinted eye protection and face shields. which will cause a steam explosion. a satisfactory period of flame heating must be established. Employees working on the charging platform or surrounding catwalks should be well trained in order to recognize the symptoms of carbon monoxide poisoning. they should wear safety helmets and. which may leak from the charging doors and be blown back by local eddy currents. Tappers and supervisors must ensure that any person not involved in the operation of the cupola remains outside the danger area. The ladle must be dried before filling with molten metal. The period of use must be based on experience with durability of refractories and on engineering recommendations. Carbon monoxide is invisible. Precautions should also be taken to prevent the discharge of material through the charging doors at such times. such as jammed cupola bottom doors. odourless and can quickly produce toxic ambient levels. Cupola repair necessarily involves the presence of employees inside the cupola shell itself to mend or renew refractory linings. aluminized clothing such as aprons. which is delineated by a radius of about 4 m from the cupola spout. gaiters or spats . Cupolas are usually sited in pairs or groups. When the cupola run is at an end. The eye protectors should resist both high velocity impact and molten metal. All work should be supervised. A refractory floor or layer of dry sand on which to drop the debris is essential. the cupola bottom is dropped to remove the unwanted slag and other material still inside the shell before employees can carry out the routine refractory maintenance. extensive exposure to which can cause cataracts. to prevent steam explosions. and operators should be instructed in their use. Extreme caution should be exercised in order to prevent remaining molten slag (the unwanted debris removed from the melt with the aid of the limestone additives) and metal from coming into contact with water.

moulds may be poured on a foundry floor and allowed to burn off there. In foundries with roof fans for exhausting pouring operations. the assembled mould moves along a mechanical conveyor to a ventilated pouring station. Typically. smoke. or it can be automatic.(lower-leg and foot coverings) and boots. generating large amounts of carbon monoxide. Pattern making Pattern making is a highly skilled trade translating the two-dimensional design plans to a threedimensional object. Where large ladles are slung from cranes or overhead conveyors. In this situation. The primary hazard control for mould burn off is a locally exhausted pouring station and cooling tunnel. high metal fume concentrations may be found in the upper regions where crane cabs are located. Pouring into the mould ignites and pyrolyses organic materials. High standards of housekeeping and exclusion of water to the highest degree possible are needed in all areas where molten metal is being manipulated. the ladle should be equipped with a mobile exhaust hood. Here. In production foundries. If the cabs have an operator. an indexing ladle controlled from a cab. Tapping and transport of molten iron and charging of electric furnaces creates exposure to iron oxide and other metal oxide fumes. . It is important that the employees are aware of the advantages of using such protection. Pouring may be from a manually controlled ladle with mechanical assist. Traditional wooden patterns are made in standard workshops containing hand tools and electric cutting and planing equipment. Moulds containing large polyurethane bound cold box cores release a dense. all reasonably practicable measures should be taken to reduce the noise to the greatest extent possible. In smaller. Employees must be well versed in normal operating procedure and should also be instructed in the hazards inherent in the work. Hooks holding molten metal ladles must be periodically tested for metal fatigue to prevent failure. positive ladle-control devices should be employed to ensure that spillage of metal cannot occur if the operator releases his or her hold. The poured mould proceeds along the conveyor through an exhausted cooling tunnel until shakeout. job shop foundries. conditioned air. carcinogenic polynuclear aromatic hydrocarbons (PAHs) and pyrolysis products from core materials which may be carcinogenic and also respiratory sensitizers. irritating smoke containing isocyanates and amines. Power-driven wood cutting and finishing machines are obvious sources of danger. Use of protective equipment should be mandatory. and there should be adequate instruction in its use and maintenance. the cabs should be enclosed and provided with filtered. and suitable ear protectors must be provided. and often suitable guards cannot be fitted without preventing the machine from functioning at all. the pouring station is provided with a compensating hood with a direct air supply.

moulding. the moulds are enclosed in metal or wooden frames called flasks. The bottom half of the pattern is placed in the bottom flask (the drag). and then the two halves of the mould assembled and fastened together. and first fine sand and then heavy sand are poured around the pattern. Casting in permanent metal moulds. sand slinger or pressure process. in which case the dust hazards of the sand foundry are still present. especially in the aluminium foundry industry. In this case. which are the pathway for the molten metal to flow into the mould cavity. coal dust. but are replaced by the risk inherent in the use of some sort of refractory material to coat the die or mould. Permanent moulds or the lost foam process may also be used. pouring and shakeout are integrated and mechanized. coating the mould in order to achieve a casting with a finer surface finish. and is therefore less likely to be a significant source of respirable dust. Chemicals are sometimes sprayed onto the mould surface. and the mould assembled by mechanical means. In certain industries using hard woods. pattern making is largely replaced by engineering methods and is really a die manufacture operation. cores are placed in the drag flask. The sand is compacted in the mould by a jolt-squeeze. a type of pneumoconiosis. has been an important development in the foundry industry. the core inserted. Most of the pattern-making hazards and the risks from sand are eliminated. Moulding sand is usually either damp or mixed with liquid resin. In manual mouldmaking. Sand from shakeout is recycled back to the sand mix operation. and all employees involved in applying these coatings should be provided with fire-retardant protective clothing and hand protection. in the larger. This involves an immediate fire risk. mould assembly. nasal cancer has been observed. Efficient ventilation systems should be fitted to eliminate wood dust from the pattern shop atmosphere. which is then burned off to leave the compound. as in die-casting. patterns (and their moulds) are made in two parts. Wooden spacers are placed in the cope to form the sprue and riser channels. The top flask (the cope) is prepared similarly. where water and other additives are added and the sand is mixed in mullers to maintain the desired physical properties.Wood sawing can create dust exposure. These methods and their hazards will be discussed under coremaking. suspended or dissolved in isopropyl alcohol. cold self-setting and gas-hardened. This has not been studied in the founding industry. Respirable talc causes talcosis. Parting agents are more widespread where hand moulding is employed. increasing use is made of sand cores. sand mix. clay and organic binders. The patterns are removed. the cope and drag flasks are prepared on a mechanical conveyor. Moulding The most common moulding process in the iron founding industry uses the traditional ―green sand‖ mould made from silica sand. Other methods of mould production are adapted from coremaking: thermosetting. as organic solvents can also cause dermatitis. A parting agent such as talc is sometimes added to promote the ready removal of the pattern from the mould. Coatings should be applied in a ventilated booth to . In production foundries. In production foundries. usually a type of graphite. For ease of assembly. ready for pouring. more automatic processes they are rarely seen. Silica dust is a potential problem wherever sand is handled. In modern die-foundry work.

core mixtures comprised sand and binders. the core hardens considerably and can be pushed clear of the pattern plate by ejector pins. local exhaust at the corebox. The sand was packed in a core box with a cavity in the shape of the core. enclosure and local exhaust at the core storage station and low-formaldehydeemission resins. Satisfactory control is difficult to achieve. which is a probable carcinogen. urea. Resin sand is injected into a metal pattern (the core box). the finished oil sand cores can still give rise to a small amount of smoke. Shell moulding uses a urea. however. Cores may be treated with a ―flare-off coating‖ to improve the surface finish of the casting.prevent the organic vapours from escaping into the workplace. and the larger storage vessels should be kept well away from the burning-off process. Medical surveillance for respiratory conditions should be provided to coremaking workers. Hot box or shell moulding and coremaking are thermosetting processes used in iron foundries. Normally. Standardized designs are available for enclosures of mixers. The core must withstand the casting process but at the same time must not be so strong as to resist removal from the casting during the knocking-out stage.or phenol-formaldehyde resin. and then dried in an oven. Hot box and shell coremaking generate substantial exposure to formaldehyde. Strict precautions should also be observed to ensure that the isopropyl alcohol is stored and used with safety. They are often lifted. conveyors and pouring and shakeout stations with appropriate exhaust volumes and capture and transport velocities. Hot boxes typically use a furfuryl alcohol (furan). such as the water jacket of an engine block. molasses or dextrin (oil sand). convection currents within the oven will be sufficient to ensure satisfactory removal of fumes from the workplace. Back injuries are common. well maintained chimney system. depending on the system. After a short curing time. but the hazard is minor. It should be transferred to a small vessel for immediate use. small amounts of acrolein in the fumes may be a considerable nuisance. Phenol. such as linseed oil. or resin-coated sand may be shipped in bags for addition to the coremaking machine. Adherence to such designs and strict preventive maintenance of control systems will attain compliance with international recognized limits for dust exposure. although they contribute enormously to air pollution After removal from the oven. moved and stacked by hand. as are the moulding boxes or flasks. which calls for the same precautions as in the case of moulds.or phenol-formaldehyde thermosetting resin. Control measures for formaldehyde include direct air supply at the operator station. Manual mould making can involve the manipulation of large and cumbersome objects. Prior to the 1960s. The moulds themselves are heavy.or urea-formaldehyde resin . New sand may be mixed with resin at the foundry. in some cases. and other contaminants. Core ovens evolve harmful pyrolysis products and require a suitable. Coremaking Cores inserted into the mould determine the internal configuration of a hollow casting. The pattern is then heated—by direct natural gas fires in the hot box process or by other means for shell cores and moulding. and power assists are needed so employees do not need to lift objects too heavy to be carried safely.

liquid or gas. such as cylinder storage. Gas-hardened coremaking comprises the carbon dioxide (CO2)-silicate and the Isocure (or ―Ashland‖) processes. A readily available eye-wash fountain should be located in any foundry area where sodium silicate is used. The catalysts for the phenol and oil isocyanate resins are usually aromatic amines based on pyridine compounds. The Isocure process is used for cores and moulds. if inhaled. alkyd and phenolic isocyanates. the core is cured by passing carbon dioxide through the core mixture. which are also toxic. Most general housekeeping principles should be strictly applied to resin moulding processes. Fascold. This forms sodium carbonate and silica gel. is mixed with a di-isocyanate (e. valve maintenance. a great many housekeeping precautions should be taken. This process has generally been used for the production of medium to large moulds and cores.g. but the greatest caution of all should be exercised when handling the catalysts used as setting agents. They can cause severe skin irritation and renal and hepatic damage and can also affect the central nervous system. usually modified by adding such substances as molasses as breakdown agents. accidents during transport or use should be adequately guarded against. Where it is supplied in cylinders or pressure tanks. Gloves and protective goggles are advisable when handling or using these compounds. and can be harmful if it comes into contact with the skin or eyes or is ingested. can act as a respiratory irritant or sensitizer. frequently phenol-formaldehyde.and phenol-formaldehyde resins with and without furfuryl alcohol. MDI) and sand. causing asthma. to cause the crosslinking. are highly volatile liquids with a strong smell of ammonia. and LEV should be provided at the mixing. It is advisable to provide an emergency shower close to areas where large quantities of sodium silicate are handled and gloves should always be worn. casting and knockout stages.contact with the skin or eyes must be prevented because the resins are irritants or sensitizers and can cause dermatitis. This is a gas-setting system in which a resin. self-set silicates. cement sand and fluid or castable sand. handling and so on. which are liquids with a pungent smell. especially where the material is stored in bulk. which. There is a very real risk of fire or explosion.. The core sand is a mixture of sodium silicate and silica sand. Copious washing with water will help to avoid the problem. The . For certain other no-bake processes the catalysts used are phosphoric or various sulphonic acids. There is also the risk from the gas itself. Inoset. Many variations of the CO2-silicate process have been developed since the 1950s. The CO2 can be supplied as a solid. The amines. Cold-setting hardeners do not require external heating to set. The isocyanates themselves should be carefully stored in sealed containers in dry conditions at a temperature between 10 and 30°C. Cold-setting (no-bake) hardening systems presently in use include: acid-catalyzed urea. which acts as a binder. often sold in drums. and extreme care should be taken. moulding. These compounds are supplied either as separate additives (three-part binder) or are ready mixed with the oil materials. After the core box is filled. usually either triethylamine or dimethylethylamine. This is injected into the core box and then gassed with an amine. since it can lower the oxygen concentration in the air in enclosed spaces. setting reaction. Empty storage vessels should be filled and soaked for 24 hours with a 5% sodium carbonate solution in order to neutralize any residual chemical left in the drum. Sodium silicate is an alkaline substance. The isocyanates employed in binders are normally based on methylene diphenyl isocyanate (MDI).

although offgassing of amine from manufactured cores is also significant. Shakeout. which is a tripping hazard. typically exposing operators well above 90 dBA over an 8 hour working day. Frequently the moulding box.and phenol-formaldehyde resins can release free phenols.. and of dust. with excess amine scrubbed through an acid tower. The sugars added to increase collapsibility produce significant amounts of carbon monoxide. No-bakes will release isocyanates (e. It is not known whether these coatings will have an inhibiting or accelerating effect on lung-tissue lesions. no-bakes. This is a noisy process. the rough casting must be removed from the mould. Leakage from the corebox is the principle cause of high exposure. The main bulk of the mould is separated from the casting usually by jarring impact. the new core binders have on the health of the de-coring operator in particular. Should some of the amine come into contact with the eyes or skin. creating less dust. all undergo some type of thermal decomposition when exposed to the temperatures of the molten metals. Sometimes hydroblasting can be used instead of a grid. casting extraction and core knockout After the molten metal has cooled. Fettling (cleaning) . urea. The casting is then removed and transferred to the next stage of the knockout operation. which can be resuspended to pose an inhalation hazard. paralysis and. aldehydes and carbon monoxide. occasionally. Great care should be taken at all times when handling this material.and phenol-formaldehyde resins. Eye protection is needed. It is feared that the reaction products of phosphoric acid may liberate phosphine. furfuryl alcohol and phosphoric acid. Relatively few studies have been carried out to determine what effect. first-aid measures should include washing with copious quantities of water for at least 15 minutes and immediate medical attention. or merely dumped. Hearing protectors should be provided if it is not practicable to reduce the noise output. The furanes. which produces less dust. death. Often small castings can be removed from the flask by a ―punch-out‖ process before shakeout. treatment and re-use. The core is removed here. the amine is applied as a vapour in a nitrogen carrier. also sometimes using high-pressure water streams.g. where they can cause convulsions. Urea. The metal and sand remain very hot. MDI) and carbon monoxide. if any. and suitable exhaust ventilation equipment should be installed to remove vapours from the working areas.characteristic effect of these amines is to cause halo vision and corneal swelling. In the Isocure process. sodium silicate and carbon dioxide. Animal experiments and some selected studies have shown that the effect of the silica dust on lung tissue is greatly accelerated when silica has been treated with a mineral acid. No studies have yet been conducted on the effect of the resin-coated silica particle on the development of pneumoconiosis. The sand then drops through the grid into a hopper or onto a conveyor where it can be subjected to magnetic separators and recycled for milling. although they also affect the central nervous system. modified linseed oil and MDI. mould and casting are dropped onto a vibrating grid to dislodge the sand (shakeout). Walking and working surfaces must be kept free of scrap. The sand gives rise to hazardous silica dust levels because it has been in contact with molten metal and is therefore very dry.

feeders and sprue in order that it be filled with metal to complete the cast object. the United Kingdom) because of the silicosis risk as the sand particles become finer and finer and the respirable fraction thus continually increases. and no operator is required inside the unit. arc-air. removal of adherent moulding sand. rough edges. Tumbling barrels generate high noise levels. Dressing methods in steel. Sprue removal is done by hand. Sprue removal is the first dressing operation. The sprue usually can be removed during the knockout stage.. Only when there is a breakdown or deterioration of the shot-blast cabinet and/or the fan and collector is there a dust problem. Hot metal fragments are thrown off and pose an eye hazard. The casting must be free of visible dust. Airless shot blasting or tumbling of castings before chipping and grinding is needed to prevent overexposure to silica dust. and the hand cleaning of the casting using hand chisels. Sand blasting has been banned in several countries (e.Casting cleaning. is carried out following shakeout and core knockout. Fused sand on large steel castings may contain cristobalite. stumps of gates. · Fettling covers removal of burnt-on moulding sand. for casting repair and for cutting and washing. may be employed for burning off headers. the metal hammers can be replaced by rubber-covered ones and the conveyors lined with the same noise-damping rubber. surplus metal. Welding techniques.g. iron and non-ferrous foundries are very similar. electric arc. such as blisters. The water or shot is discharged through a gun and can clearly present a risk to . The various processes involved are variously designated in different places but can be broadly classified as follows: · Dressing covers stripping. runners. As much as half of the metal cast in the mould is not part of the final casting. which can also require LEV. The mould must include reservoirs. pneumatic tools and wire brushes. To reduce noise. Enclosures may be necessary. The blast cabinet must be exhausted so no visible dust escapes. Detached sprues should normally be returned to the charging region of the melting plant and should not be permitted to accumulate at the despruing section of the foundry. powder washing and the plasma torch. but special difficulties exist in the dressing and fettling of steel castings owing to greater amounts of burnt-on fused sand compared to iron and non-ferrous castings. which is more toxic than the quartz found in virgin sand. such as oxyacetyleneflame cutting. flash and other readily disposable matter with hand tools or portable pneumatic tools. risers. or fettling. roughing or mucking-off. although a silica hazard may still be generated by grinding if silica is burnt into the apparently clean metal surface of the casting. The shot is centrifugally propelled at the casting. usually by knocking the casting with a hammer. cavities. but sometimes this must be carried out as a separate stage of the fettling or dressing operation. Eye protection must be used. After despruing (but sometimes before) most castings are shot blasted or tumbled to remove mould materials and perhaps to improve the surface finish. scabs or other unwanted blemishes. Water or water and sand or pressure shot blasting may be used to remove adherent sand by subjecting the casting to a high-pressure stream of either water or iron or steel shot. core sand.

Fluorspar is commonly used as a flux in aluminium melting. surface disc wheels. During furnace and flue cleaning there is the hazard of exposure to vanadium pentoxide concentrated in furnace soot from oil deposits. In aluminium and magnesium foundries. incomplete combustion due to faulty burners may result in products such as carbon monoxide being released into the air. and significant quantities of fluoride dust may be released to the environment. consequently. cup wheels and cone wheels are used for a number of purposes. In certain circumstances delay bolts linked to the blast drive motor can be fitted to the doors. Light-alloy founding The light-alloy foundry uses mainly aluminium and magnesium alloys. making it impossible to open the doors until blasting has ceased. It is advisable to post a notice on the door to the booth. Abrasive wheels may be mounted on floor-standing or pedestal machines or in portable or swing-frame grinders. swing-frame grinders are used primarily on large castings that require a great deal of metal removal. Exhaust vents around the top of the pot for removing fumes are advisable. including smoothing of internal surfaces of castings. Blasting should always be carried out in an isolated. These often contain small amounts of metals which may give off toxic fumes under certain circumstances. however. Blasters’ helmets should be approved and carefully maintained. All blasting enclosures should be inspected at regular intervals to ensure that the dust extraction system is functioning and that there are no leaks through which shot or water could escape into the foundry. considerable care is required in its use. Other Foundries Steel founding Production in the steel foundry (as distinct from a basic steel mill) is similar to that in the iron foundry. The fumes should be analysed to determine their constituents where the alloy might contain such components. the metal temperatures are much higher. warning employees that blasting is under way and that unauthorized entry is prohibited. Pedestal grinders are used for smaller castings that can be easily handled. In certain cases barium chloride has been used as a flux for magnesium alloys. some of which may be carcinogenic. melting is commonly done in crucible furnaces. effective dust exhaust systems and respiratory protection are essential. consequently. This means that eye protection with coloured lenses is essential and that the silica in the mould is converted by heat to tridymite or crystobalite. enclosed space. this is a significantly toxic substance and. Light alloys may occasionally be degassed by passing sulphur dioxide or . In oil-fired furnaces. Sand often becomes burnt on to the casting and has to be removed by mechanical means. Furnace fumes may contain complex hydrocarbons. portable grinders. which give rise to dangerous dust. A variety of grinding tools are used to smooth the rough casting. two forms of crystalline silica which are particularly dangerous to the lungs.personnel if not handled correctly.

especially where alloys have a high lead composition.French chalk is used extensively in mould dressing in magnesium foundries. thus causing soiling of personal clothing. In order to reduce the cooling rate of the hot metal in the mould. Clothing coated with magnesium dust should not be stored in lockers without humidity control. which can cause chemical pneumonia from acute exposure and kidney damage and lung cancer from chronic exposure. The sulphur in contact with the metal is constantly burning. aluminium. This ―thermite‖ mixture gives off dense fumes which have been found to be innocuous in practice. pouring and finishing operations are common. Some high-duty alloys contain cadmium. the dust should be controlled to prevent talcosis. Brass and bronze foundries Toxic metal fumes and dust from typical alloys are a special hazard of brass and bronze foundries. since spontaneous combustion may occur. Overexposure to lead is frequent in melting and pouring and can also occur in grinding. The magnesium dust should be removed from the clothing. Zinc and copper fumes (the constituents of bronze) are the most common causes of metal fume fever. however. no effects on health have been observed. antimony and so on. a mixture of substances (usually aluminium and iron oxide) which react highly exothermically is placed on the mould riser. this suspicion is unfounded.chlorine (or proprietary compounds that decompose to produce chlorine) through the molten metal. Permanent-mould process Casting in permanent metal moulds. Dyes have been introduced to improve the effectiveness of these techniques. Most of the pattern making hazards are thereby removed and the risks . although this condition is a nuisance. Molten magnesium will ignite unless a protective barrier is maintained between it and the atmosphere. Certain red dyes have been found to be absorbed and excreted in sweat. Workers should be informed of the danger of a pot or ladle of molten magnesium catching fire. alarm may be caused due to suspicion of the presence of nitrogen oxides. Penetrating oils and dusting powders are employed in the inspection of lightalloy castings for the detection of cracks. Foundry workers applying the sulphur powder to the melting pot by hand may develop dermatitis and should be provided with gloves made of fireproof fabric. Exposures to lead above safe limits in both melting. although the condition has also been observed in foundry workers using magnesium. Exhaust ventilation should be installed. so considerable quantities of sulphur dioxide are given off. exhaust ventilation and respiratory protective equipment are required for this operation. In this case. When the fumes are brown in colour. Protective clothing of fireproof materials should be worn by all magnesium foundry workers. has been an important development in the foundry. Magnesium casting entails considerable potential fire and explosion hazard. pattern making is largely replaced by engineering methods and is really a die-sinking operation. as in die-casting. The lead hazard in furnace cleaning and dross disposal is particularly acute. which may give rise to a dense cloud of finely divided magnesium oxide. and wet methods should be used for dust collection. molten sulphur is widely employed for this purpose. The finely divided aluminium produced during the dressing of aluminium and magnesium castings constitutes a severe fire hazard.

increasing use is made of sand cores. The fireresistant hydraulic fluids used in the presses may contain toxic organophosphorus compounds. burns from cupola bottom drop. The inclusion of asbestos investment casting refractory materials should be eliminated due to the hazards of asbestos. molten metal burns after crane failure. these patterns are coated with a fine refractory powder which serves as a mould-facing material. and the wax is then melted out prior to casting or by the introduction of the casting metal itself. The hazard of metal fume fever from zinc fumes should be constantly controlled. cupola maintenance including bottom drop and carbon monoxide hazards during relining. nickel and chrome plating. Trichloroethylene has been used to remove the last traces of wax. this solvent may collect in pockets in the mould or be absorbed by the refractory material and vaporize or decompose during pouring. contusion and burn injuries and a lower proportion of musculoskeletal injuries than other facilities. Automotive hardware such as chrome trim is typically zinc die cast. followed by copper. electrocution from welding equipment.from sand are also eliminated but are replaced by a degree of risk inherent in the use of some sort of refractory material to coat the die or mould. and decomposition of the wax produces acrolein and other hazardous decomposition products. In addition. in which case the dust hazards of the sand foundry are still present. They also have the highest noise exposure levels. A study of several dozen fatal injuries in foundries revealed the following causes: crushing between mould conveyor cars and building structures during maintenance and trouble-shooting. and particular care should be taken during maintenance work on hydraulic systems. Wax removal presents a definite fire hazard. steam eruption in undried ladle. as must be chromic acid mist. the worker may be exposed to the mist of oils used as die lubricants and must be protected against the inhalation of these mists and the danger of oil-saturated clothing. Die casting Aluminium is a common metal in die casting. crushing from materialhandling vehicles. Foundries report a higher incidence of foreign body. mould cracking. In modern die-foundry work. in which patterns are made by injection moulding wax into a die. falls from cranes and work platforms. . Precision founding Precision foundries rely on the investment or lost-wax casting process. overflowing transfer ladle. Wax-burnout kilns must be adequately ventilated. high-oxygen atmosphere during cupola repair and carbon monoxide overexposure during cupola repair. crushing while cleaning mullers which were remotely activated. Pressure die-casting machines present all the hazards common to hydraulic power presses. Health Problems and Disease Patterns Foundries stand out among industrial processes because of a higher fatality rate arising from molten metal spills and explosions.

A major reason is the fact that automation has resulted in the employment of fewer workers in steel production and foundries. and for competent medical care when needed. Strict maintenance of all electrical equipment and proper grounding arrangements should be enforced. There is some evidence that conditions in steel foundries are more likely to cause silicosis than those in iron foundries because of the higher levels of free silica present. Provision should be made for prompt first aid. however. Electric shock may result from badly maintained or unearthed (ungrounded) electrical equipment. Badly maintained hoisting appliances may fail and cause materials to fall on workers. Dangerous gaps between the wheel and the rest at pedestal grinders should be eliminated. and in countries where processes are labour intensive. Overexposures are likely where visible dust escapes venting in shakeout. silicosis remains a major problem. Dust Dust diseases are prominent among foundry workers. and close attention should be paid to all precautions in the care and maintenance of abrasive wheels and in regulation of their speed (particular care is required with portable wheels). Suitable PPE. even for minor injuries. may be caused by badly maintained or obstructed floors. . Unprotected eyes are at risk at all stages. Slips and falls. Silicosis is the predominant health hazard in the steel fettling shop. Injuries to the feet may be caused by falling objects or dropped loads. Sprains and strains may result from overexertion in lifting and carrying. Exposures many times above the limit occur where castings are dusty or cabinets leak. should also be provided. All dangerous parts of machinery.Abrasive wheels The bursting or breaking of abrasive wheels may cause fatal or very serious injuries: gaps between the wheel and the rest at pedestal grinders may catch and crush the hand or forearm. a mixed pneumoconiosis is more prevalent in iron fettling (Landrigan et al. Workers should be instructed in correct lifting and carrying techniques and should know how to attach loads to crane hooks and other hoisting appliances. such as eye and face shields and foot and leg protection. in part because of changes in technology. the prevalence increases with length of exposure and higher dust levels. even in well-controlled cleaning operations in modern production foundries and where castings are free of visible dust. especially when carrying heavy loads. especially abrasive wheels. In most countries. should have adequate guarding. Attempts to set an exposure level at which silicosis will not occur have been inconclusive. especially portable tools. 1986). Exposure to respirable silica dust remains stubbornly high in many foundries. with automatic lockout if the guard is removed during processing. the occurrence of new cases of silicosis is declining. a move away from silica sand in foundries and a shift away from silica brick and towards basic furnace linings in steel melting. Silica exposures are often close to or exceed prescribed exposure limits. the threshold is probably less than 100 micrograms/m3 and perhaps as low as half that amount. In the foundry. sand preparation or refractory repair.

it is likely that mixed exposures are also found. showed increased deaths from lung cancer in 14 of 15 studies. A recent review of mortality studies of foundry workers. the generally applicable solution is providing good general ventilation coupled with efficient LEV. Instruction and training in their use is needed to . lung function deficits characteristic of obstruction. These resulted from exposures after the l960s and strongly suggest that the health risks prevalent in the older foundries have not yet been eliminated. may also be responsible for some of the excess mortality. bronchopneumonia and coronary thrombosis have also been reported to be associated with pneumoconiosis in foundry workers. Increased mortality from non-malignant respiratory disease was found in 8 of 11 studies. LEV is required. Brushing can also be carried out on a ventilated bench. Dust control on large castings presents a problem. tuberculosis remains an important cause of death amongst foundry workers. Hand or pneumatic chisels used to remove burnt-on sand produce much finely divided dust. Cancer of the lung. Differences in moulding and core-making chemistry. It has been suggested that metals such as chromium and nickel. high-velocity ventilation systems. dusty processes are labour intensive and the prevalence of tuberculosis in the general population is elevated. Prevention of lung disorders is essentially a matter of dust and fume control.Silico-tuberculosis has long been reported in foundry workers. Silicosis deaths were recorded as well. but considerable progress has been made with lowvolume. lobar pneumonia. Clinical studies found x-ray changes characteristic of pneumoconiosis. and increased respiratory symptoms among workers in modern ―clean‖ production foundries. Studies of the carcinogens in the foundry environment have concentrated on polycyclic aromatic hydrocarbons formed in the thermal breakdown of sand additives and binders. Portable grinding on small castings can be carried out on exhaust-ventilated benches. often associated with emphysema. occupational exposures may have played a part. although that disease has not been completely eradicated. including the American auto industry. Dust control measures are readily adaptable to floor-standing and swing-frame grinders. or ventilation may be applied to the tools themselves. sand type and the composition of iron and steel alloys may be responsible for different levels of risk in different foundries (IARC 1984). it has long been thought by many investigators that. there has been a parallel falling off in reported cases of tuberculosis. and dusts such as silica and asbestos. in some cases at least. particularly portable grinding wheels and pneumatic tools. Because high lung cancer rates are found among cleaning room workers where the primary hazard is silica. Many workers suffering from pneumoconiosis also have chronic bronchitis. Brushing off excess materials with revolving wire brushes or hand brushes also produces much dust. In countries where dust levels have remained high. Lowvolume. Where the prevalence of silicosis has declined. high-velocity systems are most suitable for some operations.

Noise levels in the fettling of steel castings may be in the range of 115 to 120 dBA. furfuryl alcohol. when necessary. The ventilation system itself may generate exposures close to 90 dBA. In one study. and generates high levels of noise. Noise and vibration The highest levels of noise in the foundry are usually found in knockout and cleaning operations. This requires training the worker to move the duct from one location to another. Welding on cast iron requires a nickel rod and creates exposure to nickel fumes. Suitable PPE that is regularly cleaned and repaired. they are higher in mechanized than in manual foundries. Welding Welding in fettling shops exposes workers to metal fumes with the consequent hazard of toxicity and metal fever. The British Steel Casting Research Association established that the sources of noise during fettling include: · the fettling tool exhaust · the impact of the hammer or wheel on the casting · resonance of the casting and vibration against its support . Dressing and fettling of very large castings where local ventilation is impracticable should be done in a separate. The plasma torch produces a considerable amount of metal fumes. ozone. A successful approach involves creating a central station for these operations and providing LEV through a flexible duct positioned at the point of welding.. isocyanates. a variety of synthetic resin systems have been introduced into foundries to bind sand in cores and moulds. These generally comprise a base material and a catalyst or hardener which starts the polymerization. the use of PPE will aid in reducing the overall dust and fume exposures. 1985). should be provided for each worker. An exhaust-ventilated bench can be provided for welding small castings. nitrogen oxide and ultraviolet radiation. depending on the composition of the metals involved. 12 out of 78 foundry workers exposed to Pepset (cold-box) resins had asthmatic symptoms.overcome the objections of workers who find these systems cumbersome and complain that their view of the working area is impaired.g. six had a marked decline in airflow rates in a challenge test using methyl di-isocyanate (Johnson et al. Since the 1950s. along with instruction in its proper use. Controlling exposures during welding or burning operations on large castings is difficult. Many of these reactive chemicals are sensitizers (e. Good general ventilation and. isolated area and at a time when few other workers are present. amines and formaldehyde) and have now been implicated in cases of occupational asthma among foundry workers. and of these. while those actually encountered in the fettling of cast iron are in the 105 to 115 dBA range.

the type of metal. This improvement is encouraging and leads to hope that.g. isocyanates. execution of work on sound-absorbing surfaces. baffles.. This is more prevalent in steel fettlers than in iron fettlers and more frequent among those using rotating tools. These include itchy. reducing time-weighted average exposures below 3 ppm has been recommended. as a last resort. such as dimethlyethylamine. the use of portable tools and other related factors. with further development. the work area available. complete enclosures. Hand-arm vibration syndrome Portable vibrating tools may cause Raynaud’s phenomenon (hand-arm vibration syndrome— HAVS). The guidelines for safe daily exposure limits should be observed and. and shortening of exposure time by changes in work operations. formaldehyde and tertiary amines. On the basis of the occurrence of these effects.000 revolutions per minute and in the range of 40 to 125 Hz. A recent study of steelworks chippers and grinders showed they were twice as likely to develop Dupuytren’s contracture than a comparison group (Thomas and Clarke 1992). Certain basic measures are available to reduce noise exposure of individuals and co-workers. partial sound-absorbing partitions. use of multiple layers of gloves or an insulating glove.000 and 3. triethylamine and so on) are irritants and have been responsible for visual symptoms among exposed workers. A fettling bench developed by the British Steel Casting Research Association reduces the noise in chipping by about 4 to 5 dBA. panels and hoods made from sound-absorbing or other acoustical materials. hazy or blurred vision or so called ―blue-grey vision‖.· transmission of vibration from the casting support to surrounding structures · reflection of direct noise by the hood controlling air flow through the ventilation system. Eye problems Some of the dusts and chemicals encountered in foundries (e. even greater noise reductions will become possible. including isolation in time and space. It is associated with carpal tunnel syndrome and degenerative changes in the joints. Vibration transmitted to the hands of the worker can be considerably reduced by: selection of tools designed to reduce the harmful ranges of frequency and amplitude. The critical vibratory rate for the onset of this phenomenon is between 2. watery eyes. tools and rest periods. direction of the exhaust port away from the hand. This bench incorporates an exhaust system to remove dust. personal protective devices may be used. HAVS is now thought to involve effects on a number of other tissues in the forearm apart from peripheral nerves and blood vessels. Noise control strategies vary with the size of the casting. Other problems .

metal. 1991). most often in the form of sheets. compressive force is applied to pre-formed blocks (blanks) of metal. is formed into specific shapes at ambient temperatures by shearing. Approximately 15% of workers in the automotive industry work in stamping operations or plants. they present workers with a panoply of hazards to safety and health. therefore. Education and training in hazard control. Because hazards continue to exist even in the most modern plants with exemplary prevention and control programmes. a cross-sectional survey found the characteristic pleural involvement in 20 out of 900 steel workers (Kronenberg et al. Cold-rolled steel is the starting material in many stamping operations creating sheet metal parts in the automotive and appliance and other industries. The shape of the final piece is . should be provided for all foundry workers with appropriate follow-up if questionable or abnormal findings are detected. FORGING AND STAMPING Robert M. usually heated to high temperatures. In forging. including a survey of symptoms. protecting the health and well-being of workers remains an ongoing challenge to management and to the workers and their representatives. pressing and stretching between dies. until recently. Conclusion Foundries have been an essential industrial operation for centuries. Park Process Overview Forming metal parts by application of high compressive and tensile forces is common throughout industrial manufacturing. In stamping operations. Asbestos has been used widely in the foundry industry and. The compounding effects of tobacco smoke on the risk of respiratory problems among foundry workers mandate inclusion of advice on smoking cessation in a programme of health education and promotion. remain a constant necessity. usually in a series of one or more discrete impact steps. Despite continuing advances in technology. also in one or more discrete pressing steps. chest x rays. This remains difficult both in industry downturns (when concerns for worker health and safety tend to give way to economic stringencies) and in boom times (when the demand for increased output may lead to potentially dangerous short cuts in the processes). Exposures many times above the limit may be found where hazard control is poor.Formaldehyde exposures at or above the US exposure limit are found in well-controlled hot-box core-making operations. pulmonary function tests and audiograms. both among production workers and maintenance workers who have been exposed to asbestos. strips or coils. Its effects have been found in x-ray surveys of foundry workers. it was often used in protective clothing for heat-exposed workers. Periodic examinations Preplacement and periodic medical examinations.

1 Press forging Die lubricants are sprayed or otherwise applied to die faces and blank surfaces before and between hammer or press strokes.1). ring gears. causing hearing loss and possible cardiovascular illness. Catastrophic injuries resulting from unanticipated machine movements are common in stamping and forging. where continuous applications of force are used and the operator turns the part. extruding). High-strength machine parts such as shafts. steam or air hammer) operations. slow. which is then dropped by gravity or is driven by steam or air. Press forges use a mechanical or hydraulic ram to shape the piece with a single. High-impulse vibration and noise are present in most stamping and some forging (e. It can be done hot or at normal temperatures (cold-forging. The operator often holds the cold end of the stock while operating the drop hammer. Figure 82. bolts and vehicle suspension components are common steel forging products. these are among the highest-noise industrial environments (over 100 dBA). High-strength aircraft components such as wing spars. Working Conditions Many hazards common in heavy industry are present in stamping and forging operations. These can be due to: (1) mechanical failure of machine control systems. turbine disks and landing gear are forged from aluminium. With closed impression dies. (2) deficiencies in machine design or . Press forging is usually controlled automatically. as in drop hammer forging. such as clutch mechanisms in situations where workers are routinely expected to be within the machine operating envelope (an unacceptable process design). Drop hammer forges use a steam or air cylinder to raise the hammer. With open impression dies.. but is less common today.g. worker energy loads can be high. the blank is compressed between one die attached to the bottom anvil and the vertical ram. controlled stroke (see figure 82. depending on the parts handled and machine cycling rates. as in press forging. Press operators in automotive stamping plants have rates of RSIs that are comparable to those of assembly plant workers in high-risk jobs. Drop hammer forging once comprised about two-thirds of all forging done in the United States. titanium or nickel and steel alloys.determined by the shape of the cavities in the metal die or dies used. Heavy parts place workers at risk for back and shoulder problems as well as upper extremity musculoskeletal disorders. A variation on normal forging is rolling. the blank is compressed between the bottom die and an upper die attached to the ram. Approximately 3% of automotive workers are in forging operations or plants. As in other forms of automation-driven systems. The number and force of the hammer blows are manually controlled by the operator. These include repetitive strain injuries (RSIs) from repeated handling and processing of parts and operation of machine controls such as palm buttons.

alkanolamines.e. Health and Safety Problems Stamping Stamping operations have high risk of severe laceration due to the required handling of parts with sharp edges. animal and vegetable fatty acid derivatives.05 to 4. The material is sprayed or rolled onto sheet metal and further mists are generated by the stamping event itself. However. Chemical hazards specific to stamping typically arise from two main sources: drawing compounds (i. indicating that up to 2. usually without intermediate washing. although these levels tend to be lower on average (0. Mists from machine lubricating oils generated during normal operation are another generic health hazard in stamping and forging press operations powered by compressed air.. The result is haze visible in many stamping plant welding areas. Exposures most likely to present hazards are chlorinated oils (possible cancer. Possibly worse is the handling of the scrap resulting from cut-off perimeters and punched out sections of parts.g. cellulose-derived thickeners. including parts transfer automation and the functions of other connected machines.performance that invite unprogrammed worker interventions such as moving jammed or misaligned parts. liver disease. Drawing compounds (DCs) are required for most stamping. Components include petroleum oil fractions. drawing compounds may be straight oils or oil emulsions (soluble oils). Elevated digestive cancer has been observed in two automotive stamping plants.0 mg/m3. rosin or tall oil fatty acid derivatives (sensitizers). This produces emissions that include metal fumes and pyrolysis and combustion products from drawing compound and other surface residues. possibly. Typical (primarily resistance) welding operations in stamping plants generate total particulate air concentrations in the range 0. skin disorders). potentially putting workers at risk for respiratory. Most automated machine networks are not configured for quick. petroleum sulphonates. Air concentrations of mist in stamping operations may reach those of typical machining operations. The presence of chlorinated . visible fog and accumulated oil film on building surfaces are often present. borates. dermatological and digestive diseases. die lubricants) in actual press operations and welding emissions from assembly of the stamped parts. formaldehyde (from biocides) and nitrosamines (from alkanolamines and sodium nitrite. Metal content (as fumes and oxides) usually makes up less than half of that particulate matter. either as DC ingredients or in surface coatings on incoming steel). and skin contact may be higher due to extensive handling of parts. efficient and effective lockout or safe trouble-shooting. Microbiological blooms in systems that apply DCs by rolling it onto sheet metal from an open reservoir can pose risks to workers for respiratory and dermatological problems analogous to those in machining operations. special lubricity agents (e.05 to 2. chlorinated oils and waxes). Welding of stamped parts is often performed in stamping plants. petroleum fractions (digestive cancers) and.0 mg/m3). high-risk maintenance procedures performed without adequate lockout of the entire machine network involved. corrosion inhibitors and biocides.0 mg/m3 is poorly characterized chemical debris. Scrap is typically collected by gravity-fed chutes and conveyors.. Clearing occasional jams is a high-risk activity. Like other metalworking fluids. or (3) improper.

sodium nitrite. usually done manually. Additional factors in heat stress are the worker’s metabolic load during manual handling of materials and. sulphonate emulsifiers. polymeric thickeners. Roll application in stamping is preferred . furnaces for heating parts (for forging and annealing) as well as bins of hot forgings are usually nearby. Excess rates of lung cancer have been observed among welders in an automotive stamping plant. it was lubricated for shearing or sawing (as in the case of bar stock). silicone oils and biocides. An elevated lung cancer rate was observed among forging and heat treatment workers from two ball-bearing manufacturing plants. heat from combustion products of oil-based die lubricants. Forging Like stamping. unlike stamping. sodium carbonate. adds further concern. prior to forging. Die lubrication is required in most forging and has the added feature that the lubricant comes in contact with high-temperature parts. often pose higher exposures to these same air contaminants. causing injury. As a result. In forging. Comprehensive characterization of the toxicity potential of most routine operations. the worker grasps the working piece with tongs during the pressing or impact steps. total particulate air concentrations in forging operations typically range from 0. High impact forging can also eject fragments. scale or tools. In some forging activities. petroleum fractions. sodium nitrate.1 to 5. While probably adequate in some circumstances. or they are induction furnaces. forging operations can pose high laceration risks when workers handle forged parts or trim the flash or unwanted edges off parts. by swab. Furnaces used for heating metal to be forged are usually fired by oil or gas. has not been done. increasing the risk for musculoskeletal injuries. Welding production repair activities. Health and Safety Practices Few studies have evaluated actual health effects in workers with stamping or forging exposures.0 mg/m3 in the US.0 mg/m3 and vary widely within forging operations due to thermal convection currents. Some reduction in die lubricant mist concentrations is possible with careful management of the application procedure in both stamping and forging. some of which are then welded over. paint and epoxy-like adhesives). regulation of these exposures defaults to generic dust or total particulate standards such as 5. These create potential for high heat stress conditions. sodium silicate. Evaluating the longterm health effects of die lubrication technology developed in the 1960s and 1970s has only recently become feasible. in some applications. Forging die lubricant ingredients can include graphite slurries. including identification and measurement of priority toxic agents. such as oil or corrosion inhibitors. In the US. Emissions can result from fuel-fired furnaces with inadequate draft and from non-ventilated induction furnaces when incoming metal stock has surface contaminants. in some cases. This causes immediate pyrolysis and aerosolization not only in the dies but also subsequently from smoking parts in cooling bins. or if. These are applied as sprays or. this standard is not demonstrably adequate for many stamping and forging applications.derivatives and other organic ingredients raises serious concerns over the composition of welding smoke in these settings and strongly argues for ventilation controls. Application of other materials prior to welding (such as primer.

Some forging plants historically have caused acute degradation of local air quality with forging smoke and scale dust. washing parts prior to welding is highly desirable. PPE needed includes head protection. Platcow and G. Lyndon. switching from hammer to press forging when possible and adjusting the work rate to ergonomically practical levels can reduce the number of musculoskeletal injuries. and using minimal air pressure in sprays is beneficial. hearing protectors (around are as with excessive noise). Controls to reduce heat stress in stamping and hot forging include minimizing the amount of manual material handling in high-heat areas. foot protection. with appropriate air cleaning capacity. The location of cooling fans should be an integral part of the design of air movement to control mist exposures and heat stress.and oil-proof aprons and leggings (with heavy use of oil-based die lubricants) and infrared eye and face protection (around furnaces). well-designed enclosures and quieting of furnace blowers. A hearing conservation programme should be instituted. Environmental Health Hazards The environmental hazards arising from stamping plants. goggles. include disposal of waste drawing compound and washing solutions and the exhausting of welding smoke without adequate cleaning. providing protection against both laceration and liquid saturation. WELDING AND THERMAL CUTTING Philip A. Noise levels can be reduced through a combination of switching from hammer to press forges when possible. Disposition of stamping scrap and forging scale containing die lubricants is another potential issue. Lyndon* *This article is a revision of the 3rd edition of the Encyclopaedia of Occupational Health and Safety article ―Welding and thermal cutting‖ by G.when feasible. air clutches. shielding of furnaces to reduce radiation of heat. relatively minor compared to those from some other types of plants.S. Mechanization of material handling. air leads and parts handling. otherwise. and partial enclosures with LEV would reduce smoke levels substantially. Enclosures with negative pressure and mist collectors can be highly effective but may be incompatible with parts handling. cooling may be obtained only at the expense of higher exposures.S. Process Overview . However. For stamping plant welding. Possible elimination of priority hazardous ingredients should be investigated. this need not occur. minimizing the height of furnace doors and slots and using cooling fans. heat. Skin contact in stamping operations can be reduced with automation and good personal protective wear. Filtering air released from high-pressure air systems in presses would reduce press oil mist (and noise).

and become forged together. causing a joint to be formed. explosions Flux-shielded arc welding Shielded metal arc welding Uses a consumable electrode consisting of a metal (SMAC). manual metal arc welding (MMA). nitrogen dioxide. In flame gouging. fluorides (especially with low-hydrogen electrodes). fire. Table 82. resistance heating and induction heating. carbon monoxide. nitrogen dioxide. burns. electrical resistance offered to passage of current between two or more workpieces. carbon monoxide. burns infrared radiation. Soldering Similar to brazing. or both.6). explosions Gas pressure welding Metal fumes. Metal cutting and flame gouging Metal fumes. struck between an electrode and a workpiece or between two electrodes 3. In one variation. lead fumes. fire. burns infrared radiation. carbon monoxide. Heating is also done using a soldering iron. burns infrared radiation. Description Hazards Metal fumes. fire. Other sources of heat for welding are discussed below (see table 82. infrared and ultraviolet radiation. fire. The melting temperature of the filler metal is above 450 °C. Heating is done by flame heating. noise. The three common direct sources of heat are: 1. . burns Brazing The two metal surfaces are bonded without melting the metal. burns of the filler metal is below 450 °C. except the melting temperature Fluxes. electrical arc. noise. flame produced by the combustion of fuel gas with air or oxygen 2. noise. open arc Metal fumes. and a jet of pure oxygen is directed onto the point of cutting and moved along the line to be cut. a strip of surface metal is removed but the metal is not cut through. The parts are heated by gas jets while under pressure. explosion.6 Description and hazards of welding processes Welding Process Gas welding and cutting Welding The torch melts the metal surface and filler rod. "stick" arc core surrounded by a flux coating welding.Welding is a generic term referring to the union of pieces of metal at joint faces rendered plastic or liquid by heat or pressure. the metal is heated by a flame. explosions Metal fumes (especially cadmium). fluorides. nitrogen dioxide.

metal active gas welding (MAG) Uses a flux-cored consumable electrode. electrical. No flux or filler metal is used. burns. burns. fire. fluorides. carbon monoxid (with CO2 gas). ozone. metal fumes. electrical. fluorides. noise The tungsten electrode is non-consumable. electrical. fire. ultraviolet and infrared radiation. ultraviolet radiation. gas tungsten arc welding (GTAW). noise Electric resistance welding Resistance welding (spot. noise. ozone. followed by a consumable bare metal wire electrode.400°C. nitrogen dioxid fire. The arc melts the flux to produce a protective molten shield in the welding zone. infrared radiation. During the passage of the current. The heat machinery hazards. and electrical. carbon monoxide Plasma arc welding (PAW) Similar to TIG welding. infrared radiation. The workpieces are Burns. burns. infrared radiation. electrical. burns. generated at the interface between the components electrical. infrared radiation. burns. metal fumes. stream of inert gases pass through a small orifice tungsten arc cutting before reaching the workpiece. projection or butt welding) A high current at low voltage flows through the Ozone. two components from electrodes.This is also used for metallizing. fire. except that the arc and and plasma arc spraying.welding Submerged arc welding (SAW) A blanket of granulated flux is deposited on the workpiece. noise. (with CO2 gas). fluorides. burns. ozone. nitrogen dioxide fire. with a gap between them. ozon nitrogen dioxide Fluorides. creating a "plasma" of highly ionized gas which can achieve temperatures of over 33. metal fumes copper plates or shoes are placed on one or both Electro-slag welding . also metal fumes. carbon monoxid continuously to the arc. heliarc Ultraviolet radiation. seam. infrared radiation. and filler metal is introduced as a consumable into the arc manually. fluorides. Flux core arc welding (FCAW). also noise. possible x rays Ultraviolet radiation. fire. fire. nitrogen dioxid fire. noise. gas metal arc welding (GMAC) The electrode is normally a bare consumable wire Ultraviolet radiation. metal of similar composition to the weld metal and is fed fumes. electrical. ozone. and nitrogen dioxide Gas-shielded arc welding Metal inert gas (MIG). set vertically. ozone. noise (sometimes). Tungsten inert gas (TIG). carbon monoxide. electrical. pressure by the electrodes produces a forge weld. nitrogen dioxide. metal fumes brings them to welding temperatures. Used for vertical butt welding. may have carbon dioxide shield (MAG) Metal fumes.

burns. and at forging temperature the rotation ceases. Laser welding and drilling Electrical. Laser beams can be used in industrial applications requiring exceptionally high precision. Arcair cutting Metal fumes. The molten metal produced is blown away by jets of compressed air. An arc is struck between the end of a carbon electrode (in a manual electrode holder with its own supply of compressed air) and the workpiece. fire. which is kept molten by resistance to the current passing between the electrode and the workpieces. such as miniature assemblies and micro techniques in the electronics industry or spinnerets for the artificial fibre industry.sides of the joint to form a bath. carbon monoxide nitrogen dioxide. metal a low-voltage. A forge weld is obtained by pressure. a large current flows. burns. protected by molten flux or slag. ozone. The energy of the electrons is confined spaces transformed into heat upon striking the workpiece. electrical Friction welding A purely mechanical welding technique in which Heat. burns. A pool of molten metal is formed. the molten metal and slag are retained in position by shifting the copper plates. burns. decomposition products of workpiece coatings . burns metal fumes. When the ends fumes of the components are brought into contact. Flash welding The two metal parts to be welded are connected to Electrical. ultraviolet radiation. machinery hazard one component remains stationary while the other is rotated against it under pressure. Heat is generated by friction. The laser beam melts and joins the workpieces. metal dusts. A forging pressure then effects the weld. infrared radiation. As welding progresses. causing "flashing" to occur and bringing the ends of the components to welding temperatures. high-current source. laser radiation. high voltages. fire. thus melting the metal and fusing the workpiece. fire. by a beam of electrons from an electron gun at electrical. Other welding processes Electron beam welding A workpiece in an vacuum chamber is bombarded X rays at high voltages. An arc is established under a flux layer between one or more continuously fed electrode wires and a metal plate. filling the joint and making a weld. This resistancegenerated heat melts the sides of the joint and the electrode wire.

During the welding process. Most conventional arc welding is done manually by means of a covered (coated) consumable electrode in a hand-held electrode holder. copper. In gas welding and cutting. The gun forces the stud against the plate and welds it. oxygen or air and a fuel gas are fed to a blowpipe (torch) in which they are mixed prior to combustion at the nozzle. the welding area must be shielded from the atmosphere in order to prevent oxidation and contamination. ozone. burns producing molten metal with the evolution of intense heat. the consumable electrode consists of a metal core surrounded by a flux coating material. the two pieces are generally not brought to fusion temperature (brazing. nitrogen dioxide Thermite welding A mixture of aluminium powder and a metal oxide Fire. The alloy often has a lower melting point than the parts to be joined. noise. Metal fumes. radiation.Stud welding An arc is struck between a metal stud (acting as the electrode) held in a stud welding gun and the metal plate to be joined. The flux melts as welding progresses. soldering). The crucible is tapped and the molten metal flows into the cavity to be welded (which is surrounded by a sand mould). infrared and ultraviolet radiation. In flux-shielded arc welding. etc. gauntlets and goggles In arc welding. Usually it is necessary to add molten metal to the joint either by melting the electrode itself (consumable electrode processes) or by melting a separate filler rod which is not carrying current (nonconsumable electrode processes). causing them to flow together. burns. which is usually a complex mixture of mineral and other components. fire.2). In this case. The blowpipe is usually hand held (see figure 82. infrared powder (iron.) is ignited in a crucible. electrical. The electrode can be connected to either an alternating current (AC) or direct current (DC) electric supply.2 Gas welding with a torch and rod of filter metal. This is often used to repair castings or forgings. Figure 82. the arc is struck between an electrode and the workpieces. covering the molten metal with slag and . Chemical fluxes may be used to prevent oxidation and facilitate the joining. The heat melts the metal faces of the parts to be joined. The temperature of this operation is about 4. explosion. There are two types of protection: flux coatings and inert gas shielding. A filler metal or alloy is frequently added. Welding is also accomplished by many semi or fully automatic electric welding processes such as resistance welding or continuous electrode feed. Shielding is provided by a ceramic ferrule surrounding the stud. The welder is protected by a leather apron. and raises the temperature of the ends of the components to melting point.000°C when the workpieces fuse together.

Other hazards associated with specific welding processes include electrical hazards. The gas selected depends upon the nature of the materials to be welded. heavy equipment and so on). compressed gas cylinders and explosions. oxygen and the fuel gas (acetylene. noise. nitrogen dioxide. Heat stress may result from working in warm weather and the occlusive effects of the personal protective equipment.and tungsten inert gas (MIG and TIG). Physical strain. radiant heat (infrared radiation) and inhalation of metal fumes and other contaminants. They should be connected to regulators with special canvas-reinforced hoses placed in such a way that they are unlikely to be damaged. In gas-shielded arc welding. See table 82. helium. bridges and towers.6 for additional detail. propane) are supplied to the torch from cylinders. but in the field in the construction or repair of large structures and machinery (e. carbon dioxide) generated by the heated flux. carbon monoxide. The heat generated at the interface between the components brings them to welding temperatures. A hardwood stick or soft brass wire should be used for cleaning the tips. inordinate fatigue and musculoskeletal injuries may follow being required to reach. hydrogen. For example.enveloping the welding area with a protective atmosphere of gases (e. town gas.. The special fire and explosion hazards and precautions for the safe use and storage of the fuel gases are also discussed elsewhere in this Encyclopaedia. Argon. ships. a blanket of inert gas seals off the atmosphere and prevents oxidation and contamination during the welding process. railroad engines and cars.. frameworks of buildings. set it up and work in confined spaces or on scaffolds. the slag must be removed. even without the heat generated by the welding process. The gases are stored in these cylinders at high pressure. Resistance welding involves using the electrical resistance to the passage of a high current at low voltage through components to be welded to generate heat for melting the metal. kneel or work in other uncomfortable and awkward positions. burns. Compressed gas cylinders In high-pressure gas welding installations. often by chipping. Hazards and Their Prevention All welding involves hazards of fire. ozone. ultraviolet radiation. After welding.g. · Blowpipes must be kept in good order and cleaned at regular intervals. Much welding is not done in shops where conditions can generally be controlled. The welder may have to carry all his or her equipment to the site. . nitrogen or carbon dioxide are commonly used as the inert gases. The following precautions should be observed: · Only pressure regulators designed for the gas in use should be fitted to cylinders. an acetylene regulator should not be used with coal gas or hydrogen (although it may be used with propane). fluorides.g. The two most popular types of gas-shielded arc welding are metal.

welding plant or flammable materials must be excluded from the house or from the vicinity of an open-air generator. acetylene is generally produced in generators by reaction of calcium carbide and water. In many countries. the internationally accepted colour codes used for the transport of dangerous materials are applied in this field. a hammer and chisel should never be used to open drums. · The colour coding in force or recommended for identification of cylinders and accessories should be scrupulously observed. all calcium carbide must be removed and the plant filled with water. Stores must be situated under cover. It is dangerous to leave calcium carbide drums exposed to any source of water. other electrical gear and electrical lamps should either be located outside the building or be explosion-proof. The gas is then piped to the welding or cutting torch into which oxygen is fed. away from any flammable material. Drums should be opened only immediately before the generator is charged. none of the old charge must be used again. The material should be stored and kept dry. When a generator is being recharged or cleaned. Smoking. Stationary generating plants should be installed either in the open air or in a well-ventilated building away from the main workshops. A special opener should be provided and used. Pieces of calcium carbide wedged in the feed mechanism or adhering to parts of the plant should be carefully removed. and if they adjoin another building the party wall must be fireproof. Calcium carbide is supplied in sealed drums. Adequate lighting should be provided. flames. Many of these precautions also apply to portable generators. on a platform raised above the floor level. using non-sparking tools made of bronze or another suitable non-ferrous alloy. which should be conspicuously displayed. Portable generators should be used. switches. The dismantling and servicing should be carried out only by the manufacturer of the equipment or by a specialist. Acetylene generators In the low-pressure gas welding process. All concerned should be fully conversant with the manufacturer’s instructions.· Oxygen and acetylene cylinders must be stored separately and only on fire-resistant premises devoid of flammable material and must be so located that they may be readily removed in case of fire. The water should remain in the plant for at least half an hour to ensure that every part is free from gas. The ventilation of the generator house should be such as to prevent the formation of an explosive or toxic atmosphere. cleaned and recharged only in the open air or in a well-ventilated shop. Before a generator is dismantled. The storeroom should be suitably ventilated through the roof. The case for enforcement of uniform international standards in this respect is strengthened by safety considerations bound up with the increasing international migration of industrial workers. The following precautions should also be observed: . Local building and fire protection codes must be consulted. torches.

· Suitable fire-extinguishing apparatus should always be at hand. · An explosion may be caused by ―flash-back‖. · Precautionary measures should be taken in the case of openings or cracks in walls and floors. · Fire brigades may be necessary.· A properly designed back-pressure valve must be fitted between the generator and each blowpipe to prevent backfire or reverse flow of gas. · Wood structures should be discouraged or similarly protected. Local building and fire codes should be consulted. it should never be released into the air in a confined space. tarpaulins should never be used. adequate ventilation and monitoring are required to ensure freedom from gas leaks. In these cases. · Local building and fire codes should be consulted. In gas cutting. which results from dipping the nozzle-tip into the molten metal pool. · Since explosions can occur when acetylene gas is present in air in any proportion between 2 and 80%. or from any other stoppage. · Only blowpipes of the injector type designed for low-pressure operation should be used. clothing and other materials become actively combustible in the presence of oxygen. . Fire and explosion prevention In locating welding operations. flammable material in adjoining rooms or on the floor below should be removed to a safe position. nearby objects and waste material. mud or paint. In the case of low-pressure plant using an acetylene generator. The tip should also be cooled frequently. many metals. in order to deal with any outbreak of fire. gas cutting should never be undertaken in a confined space without proper ventilation arrangements. Particles of slag or metal that become attached to the tip should be removed. The following procedures should be followed: · All combustible material must be removed or adequately protected by sheet metal or other suitable materials. consideration should be given to surrounding walls. For heating and cutting. any oxygen which may not be consumed will be released into the atmosphere. · Oxygen must be carefully controlled. a non-return valve should be placed between each blowpipe and the supply main or pipeline. and the water level checked daily. A responsible person should be assigned to keep the site under observation for at least half an hour after completion of the work. floors. For example. Water must never be used. fire extinguishers of dry powder or carbon dioxide types are satisfactory. buckets of dry sand should also be kept available. Wood floors should be avoided. Only soapy water should be used to search for gas leaks. town gas or hydrogen at low pressure are sometimes employed. The valve should be regularly inspected after backfire.

Screens also protect passers-by from eye burns. leggings overlap shoes and so on. However.· Alloys rich in magnesium or other combustible metals should be kept away from welding flames or arcs. in view of the ease with which aluminium powder will ignite. This programme outlines the precautions and procedures to be followed during welding. Explosions may be prevented either by removing any flammable material or by making it non-explosive and nonflammable. appropriate precautions should be taken in handling and storage (avoidance of exposure to high heat and possible ignition sources). Goggles made specifically for gas welding and cutting should be worn to protect the eyes from heat and light radiated from the work. It must be plant specific and may include an internal permit system that must be completed with each individual operation. a vessel should always be treated as if it had contained a flammable substance. In arc welding. If the previous contents are unknown. Protective covers over filter glass should be cleaned as required and replaced when scratched or damaged. seam or projection welds if conditions are correct. Intense infrared and visible radiation from a gas welding or cutting flame and incandescent metal in the weld pool can cause discomfort to the operator and persons in the vicinity of the operation. In overhead welding. leggings and head covering. Other types of protective clothing include leather aprons. the leather gauntlet type of glove with canvas or leather cuffs is sufficient. and burns can result from handling of hot assemblies. Loose parts . In cutting and arc welding operations. All protective clothing should be free from oil or grease. a protective cape and cap are necessary. leather shoe coverings or other suitable spats should be worn to prevent hot particles from falling into boots or shoes. a high-frequency spark used to initiate the arc can cause small. This programme should include the specific operations conducted along with the safety precautions to be implemented. spatter. Clothing should not have pockets or cuffs that could trap sparks. Heavy articles left hot on completion of welding should always be marked ―hot‖ as a warning to other workers. Protective clothing should be inspected for burst seams or holes through which molten metal or slag may enter. · A written hot-work permit programme is required for welding in some jurisdictions. burning and so on. Each operation should be considered in advance. · The mixture of aluminium and iron oxide used in thermite welding is stable under normal conditions. so as not to trap globules of molten metal. cutting. sleeves. With resistance welding. · Welding of containers can be extremely hazardous. deep burns if concentrated at a point on the skin. Where molten metal or hot particles are emitted. and it should be worn so sleeves overlap gloves. the heat produced may not be visible. Protection from heat and burn hazards Burns of the eyes and exposed parts of the body may occur due to contact with hot metal and spattering of incandescent metal particles or molten metal. but non-flammable screens should be used and precautions taken. the protective clothing being worn should deflect spatter. and the quasi-explosive nature of the reaction. The type and thickness of fire-resistant clothing worn should be chosen according to the degree of hazard. jackets. slag and so on. For protecting the hands and forearms against heat. and necessary precautions designed and implemented. Particles of hot or molten metal should not fly out of spot. and seams should be inside.

or where other portable electric tools are also in use. For electron-beam welding. Provision should be made to accommodate the electrode holder safely when not in use by means of an insulated hook or a fully insulated holder. low-voltage devices) can be installed in the welding circuit. A reliable system of grounding of all units and control cabinets is necessary. Dragging of cables and plastic gas supply tubes (gas-shielded processes) across hot plates or welds must be avoided.should not be left in the throat of the machine because they are liable to be projected with some velocity. Rubber tubes and rubber-covered cables must not be used anywhere near the high-frequency discharge. The risk of electric shock should therefore not be ignored. A well-arranged. Electrical safety Although no-load voltages in manual arc welding are relatively low (about 80 V or less). grounding should be supervised by a competent person. Vulcanized or tough rubbersheathed cables are satisfactory on the primary side. penetrating high-frequency burn. additional electrical protection (no-load. the voltages may be as high as 400 V and danger should be anticipated. secure and free from dangerous obstructions. For work in confined spaces or dangerous positions. ensuring that only extremely low-voltage current is available at the electrode holder when welding is not taking place. Cables and connections should be sound and of adequate capacity. The working position should be dry. because the ozone produced will rot the rubber. Before welding commences. To avoid this condition. Dirt and metallic or other conducting dust can cause a breakdown in the high-frequency discharge unit.) Electrode holders in which the electrodes are held by a spring grip or screw thread are recommended. Discomfort due to heating can be reduced by effective heat insulation on that part of the electrode holder which is held in the hand. properly ventilated and tidy workplace is important. Jaws and connections of electrode holders should be cleaned and tightened periodically to prevent overheating. The technique of firing the arc by a high-frequency pulse exposes the operator to the dangers of an unpleasant shock and a painful. the grounding installation on arc welding equipment should always be checked. the safety of the equipment used must be checked prior to each operation. Hearing protection should be worn when using compressed air for more than a few seconds. a system of interlocks must be fitted to the various cabinets. especially in cramped spaces or in insecure positions. To protect against electric shock. welding currents are high. and transformer primary circuits present the usual hazards of equipment operated at power supply line voltage. the unit should be cleaned regularly by blowing-out with compressed air. The cable connection should be designed so that continued flexing of the cable will not cause wear and failure of the insulation. Plastic tubes and polyvinyl chloride (PVC) covered cables should be used for all supplies from the transformer to the electrode holder. For plasma welding equipment used for cutting heavy thicknesses. The electrode lead should not come in contact with the job or any other earthed object (ground). Where two or more welding machines are grounded to the same structure. (See discussion of confined spaces below. well-lighted. A proper grounding clamp or bolted terminal should always be used. Ultraviolet radiation .

may produce a painful conjunctivitis (photo-ophthalmia) known as ―arc eye‖ or ―eye flash‖. Precautions include: · A shield or helmet fitted with correct grade of filter should be used (see the article ―Eye and face protection‖ elsewhere in this Encyclopaedia). zinc from galvanizing and copper as a thin coating on continuous mild steel filler rods) . · The face. Helmets and handshields are provided with a filter glass and a protective cover glass on the outside. · The use of black paints for the inside of welding booths has become an accepted practice. Even momentary exposure to bursts of arc flash. flat handshields provide insufficient protection from reflected radiation. This should be regularly inspected. but the paint should produce a matte finish. immediate medical attention must be sought. helmets should be used. otherwise. Excessive exposure to ultraviolet radiation may also cause overheating and burning of the skin (sunburn effect).. For the gas-shielded arc welding processes and carbon-arc cutting.g. arise from a variety of sources: · the metal being welded. permanent screens should be erected where possible. including stray flashes from other workers’ arcs. of sturdy construction and of a flame-resistant material. zinc and cadmium from plating.The brilliant light emitted by an electric arc contains a high proportion of ultraviolet radiation. nape of the neck and other exposed parts of the body should be properly protected. · All arc welding operations should be screened to protect other persons working nearby. · Welding booths and portable screens should be checked regularly to ensure that there is no damage which might result in the arc affecting persons working nearby. temporary screens should be used. All screens should be opaque. cleaned and replaced when scratched or damaged. Adequate ambient lighting should be provided to prevent eye strain leading to headaches and accidents. Filtered goggles or eyeglasses with sideshields should be worn under the helmet to avoid exposure when the helmet is lifted up for inspection of the work. especially when working close to other welders. If any person is exposed to arc flash. · Assistants should wear suitable goggles at a minimum and other PPE as the risk requires. Chemical hazards Airborne contaminants from welding and flame cutting. Where the work is carried out at fixed benches or in welding shops. the metal in the filler rod or constituents of various types of steel such as nickel or chromium) · any metallic coating on the article being welded or on the filler rod (e. Helmets will also provide protection from spatter and hot slag. including fumes and gases.

A high standard of maintenance of the motor and the battery is necessary. lead) and LEV is not practicable—for example. smoke and other irritant breakdown products) · flux coating on the filler rod (e. entanglement possibilities and so on of persons wearing respiratory protective equipment. Fumes and gases should be removed at the source by LEV.g. These may be . manganese and iron. an approved. the exhausted air should not be recirculated. in brass founding. as well as from exposure to other metals such as copper. Whenever respiratory protective equipment is to be worn. carbon dioxide. carbon monoxide. Metal fume fever Metal fume fever is commonly seen in workers exposed to the fumes of zinc in the galvanizing or tinning process.g. phosgene) · inert gas used as a shield (e. In such circumstances. This can be provided by partial enclosure of the process or by the installation of hoods which supply sufficiently high air velocity across the weld position so as to ensure capture of the fumes. in the welding of galvanized metal and in metallizing or metal spraying. as well as to protection from the hazard of ozone. plutonium and so on).. argon).g.. inorganic fluoride) · the action of heat or ultraviolet light on the surrounding air (e. In general. When there is a risk to health from toxic fumes (e. Special attention should be paid to ventilation in the welding of non-ferrous metals and certain alloy steels. grease.· any paint. nitrogen dioxide. care must be taken to protect the operator from any dust cloud when opening the chamber. It is an acute condition that occurs several hours after the initial inhalation of particles of a metal or its oxides. It should be recirculated only if there are not hazardous levels of ozone or other toxic gases and the exhaust air is filtered through a highefficiency filter.. Portable as well as fixed ventilation systems are readily available. beryllium. With electron-beam welding and if materials being welded are of a toxic nature (e. carbon monoxide and nitrogen dioxide which may be formed. ozone) or on chlorinated hydrocarbons (e. It occurs in new workers and those returning to work after a weekend or holiday hiatus. highefficiency full-facepiece respirator or ahigh-efficiency positive pressure powered air-purified respirator (PAPR) should be worn. the safety of the workplace should be reviewed to determine whether extra precautions are necessary. bearing in mind the restricted vision. especially with the original high-efficiency positive pressure power respirator. when lead-painted structures are being demolished by flame cutting—the use of respiratory protective equipment is necessary. It starts with a bad taste in the mouth followed by dryness and irritation of the respiratory mucosa resulting in cough and occasionally dyspnoea and ―tightness‖ of the chest.g.g... helium.g. The use of positive pressure compressed air line respirators should be encouraged where a suitable supply of breathing-quality compressed air is available... carbon dioxide. debris and the like on the article being welded (e.g.

(See figure 82. Any parts of the machine providing shields against x-ray radiation should be interlocked so that the machine cannot be energized unless they . See the chapter Radiation. manholes. the plasma jet is ejected at very high speeds. Gas-shielded arc welding processes can decrease the oxygen content of the air. and recovery is usually complete in about 24 hours with no residua. including plasma welding.accompanied by nausea and headache and. some types of resistance welding machines and gas welding. may be required and is highly recommended for work that must be carried out in spaces that are typically not constructed for continuous occupancy. Workers must be kept at a safe distance from such equipment. Ventilation of confined spaces is crucial. chills and fever which may be quite severe. toxic. Gilman Noise Noise is a hazard in several welding processes. Confined spaces For entry into confined spaces. producing intense noise (up to 90 dBA). There is no particular treatment. but are not limited to. Local and governmental regulations must be followed. including audiometric (hearing capacity) examinations and employee training. there may be a risk of the atmosphere being explosive. Sufficient shielding must be provided with electron-beam welding to prevent x rays from penetrating the walls and windows of the chamber. particularly in the higher frequency bands.) Figure 82. some 10 to 12 hours after the exposure.3 Welding in an enclosed space S. Any such confined space must be certified by a responsible person as safe for entry and for work with an arc or flame. A confined-space entry programme. To prevent hearing damage. ear plugs or muffs must be worn and a hearing conservation programme should be instituted. ship holds and the like. including an entry permit system. oxygen deficient or combinations of the above. ionizing elsewhere in this Encyclopaedia. the customary warning notices and instructions must be strictly observed. Ionizing radiation In welding shops where welds are inspected radiographically with x-ray or gamma-ray equipment. sleep and often by polyuria and diarrhoea. These last several hours and are followed by sweating. In plasma welding. since gas welding not only produces airborne contaminants but also uses up oxygen.F. Examples include.3 . The use of compressed air to blow off dust also creates high noise levels. It can be prevented by keeping exposure to the offending metallic fumes well within the recommended levels through the use of efficient LEV. vaults. Radioactive sources must be handled only with the required special tools and subject to special precautions.

and regularly thereafter. surface quality. and also by choosing the appropriate tool cutting-edge geometry and material. LATHES Toni Retsch* *Adapted from the 3rd edition. with the spindle and chuck . the eyes should be protected by goggles or other means. and the feed and traverse movements are produced by the tool. By varying these three basic movements. The important part lathes play in metalworking shops is best illustrated by the fact that 90 to 95% of the swarf (metal shavings) produced in the valves and fittings industry originates from lathes. Lockout/tagout procedures should be used when machinery with electrical. shape of the chip formed and tool wear. About one-tenth of the accidents reported in this industry are due to lathes. Cuts and lacerations can be minimized by first deburring components and by wearing protective gloves or gauntlets. lathes rank fifth after woodworking machines. If a machine is operated while a finger or hand is lying between the electrodes. According to a study of the relative accident frequency per machine unit carried out in a plant manufacturing small precision parts and electrical equipment. which moves with considerable force. Structure of Lathes A typical lathe consists of: · a bed or base with machined slideways for the saddle and tailstock · a headstock mounted on the bed. metal-cutting saws. it is possible to influence the rate of stock removal. severe crushing will result. this corresponds to one-third of all machine accidents. The cutting movement is produced by rotating the workpiece.are in position. Where possible. Encyclopaedia of Occupational Health and Safety. power presses and drilling machines. mechanical or other energy sources is being maintained or repaired. The need for protective measures on lathes is therefore beyond doubt. a suitable means of guarding must be devised to safeguard the operator. When slag is being removed from welds by chipping and so on. Turning is a machine process in which the diameter of material is reduced by a tool with a special cutting edge. Other hazards Resistance welding machines have at least one electrode. Machines should be checked at the time of installation for leaks of x-ray radiation.

It is . It corresponds to the basic model with horizontal turning axis. · Turret lathe. The work is held between centres. threading machines This basic model of a lathe can be infinitely varied. by a faceplate or in a chuck. Machines of this type enable a workpiece to be machined by several tools which are engaged one after the other. which rotates for bringing them into cutting position. The various operations. thanks to the great versatility and easy programmability of the control system. · Copy-turning lathes. there is a trend in evolution from interpolation-programmed to memory-programmed controls. · Vertical lathe (boring and turning mill). Figure 82. · Automatic lathe.4 Lathes. All the aforementioned machines can be equipped with a numerical control (NC) or computer-assisted numerical control (CNC) system. The result is a semiautomated or fully automated machine which can be used rather universally. The most important types of lathe are as follows: · Centre lathe.· a feed gearbox attached to the front of the bed for transmitting the feed movement as a function of the cutting speed through the leadscrew or feed shaft and apron to the saddle · a saddle (or carriage) carrying the cross slide which performs the traverse movement · a toolpost mounted on the cross slide (see figure 82. it is clamped to a horizontal revolving table. This enables several tools to be engaged at the same time. This is the most frequently used turning machine. including the change of the work. The work turns about a vertical axis. are automated. The desired shape is transmitted by tracer control from a template to the work. but there are also drum-type turret lathes. This type of machine is generally used for machining large castings and forgings. There are bar automatics and chucking automatics. The future development of the lathe will probably concentrate on control systems. Contact controls will be increasingly replaced by electronic control systems.4). · Multiple-tool lathe. As regards the latter. capstan lathe. from the universal machine to the special automatic lathe designed for one type of work only. The tools are held in the turret. · NC and CNC lathes. cutting-off machines. The turrets are generally of the disc or crown type.

no power disconnect switch for each machine) · missing guards or the absence of auxiliary devices (severe injuries have been caused to workers who tried to brake the spindle of their lathes by pressing one of their hands against unguarded belt pulleys and to operators who inadvertently engaged unguarded clutch levers or pedals. injuries due to flying chips because of the absence of hinged or sliding covers have also occurred) · inadequately located control elements (e.foreseeable in the long run that the use of increasingly efficient process computers will tend to optimize the machining process. free-hanging hair) · insufficient instruction of personnel (an apprentice was fatally injured when he filed a short shaft which was fixed between centres and rotated by a cranked carrier on the spindle nose and a straight one on the shaft... which was wrapped around the workpiece. and it projected more than 1 m beyond the headstock. when the lathe spindle started rotating.. moreover. a long bar was machined on a conventional production lathe. Accidents Lathe accidents are generally caused by: · disregard for safety regulations when the machines are installed in workshops (e. Control elements .g.g. Designers should give special attention to control and transmission elements. shortcomings from the point of view of occupational physiology) · lack of PPE or wearing unsuitable work clothing (severe and even fatal injuries have been caused to lathe operators who wore loose clothes or had long. the chuck aperture was too large for the bar and was made up by inserting wooden wedges. the free bar end bent by 45° and struck the operator’s head.g. not enough space between machines. the operator died during the following night) · defective machine elements (e. Accident Prevention The prevention of lathe accidents starts at the design stage. the lathe carrier seized his left-hand sleeve.. a loose carrier pin in a clutch may cause the lathe spindle to start rotating while the operator is adjusting a workpiece in the chuck).e. a turner’s hand can be pierced by the tailstock centre if the pedal controlling the chuck is mistaken for the one controlling the hydraulic circuit of the tailstock centre movement) · adverse conditions of work (i.. dragging the apprentice violently into the lathe) · poor work organization leading to the use of unsuitable equipment (e.g. it was too long for this lathe.

Emergency stop buttons must be easily reached and should be in red. They must be designed and located in such a way that they can be easily operated by the threatened worker. An important contribution to the prevention of lathe accidents can be made by the persons responsible for the installation of the machine. The floor on which the operator stands must be insulated against cold. and the flooring should not become slippery even when covered with a film of oil. the disconnect switch should be so designed that it can be padlocked in its out position—a safety measure against accidental reconnection. The operators should not turn their backs towards passageways. Care should be taken that the insulation forms no stumbling obstacle. Switches which monitor guards and interlock them with the machine drive should be chosen and installed in such a way that they positively open the circuit as soon as the guard is shifted from its protecting position. This means that controls must never be arranged at points which can be reached only by passing the hand over the working zone of the machine or where they may be hit by flying chips. Bar-stock guides must not protrude into the passageways. A pushbutton can be made safe by lodging it in a recess or by shrouding it with a protective collar. pulleys. . Enough space should be left for materials-handling equipment. Controls should be identified with easily readable and understandable markings. it is advisable to use symbols. gears) must be covered with guards. Hand-operated controls should be designed and located in such a way that the hand movement corresponds to the controlled machine movement. Lathes should be so installed that the operators tending them do not hinder or endanger each other. reliably cut the pneumatic and hydraulic power and vent the circuits. Protective screens should be installed where neighbouring workplaces or passageways are within the range of flying chips. the clutch engaging levers on the headstock and apron should be provided with safety locking devices or screens. for stacking workpieces and for tool boxes. On large machines. For instance. The layout of the machine controls should be such that the operator can easily distinguish and reach them.Each lathe must be equipped with a power disconnect (or isolating) switch so that maintenance and repair work may be carried out safely. Passageways must be clearly marked. To avoid misunderstandings and linguistic difficulties. The actuating elements of control gear which may trip a dangerous machine movement must be guarded so as to exclude any inadvertent operation. This switch must disconnect the current on all poles. Emergency stop devices must cause the immediate standstill of the dangerous movement. and that their manipulation presents no hazard. Transmission elements All moving transmission elements (belts.

When machining bar stock. chucks. If starting the lathe while the chuck jaws are open presents a danger. by fitting the chuck with a locking key or by securing it with a two-part locking ring. the spindle rotation must be stopped. the portion projecting beyond the lathe must be enclosed by barstock guides. it should be ensured that the jaws cannot be slung out when the lathe is started · chucks of this type should be designed in such a manner that the key cannot be taken off before the jaws have been secured. Temporary installations should be avoided. Reversing the gripping direction from inside to outside (or vice versa) while the spindle rotates must not cause the chuck to be dislodged from the spindle. If the gripping force of a power chuck diminishes. measures must be taken which make it impossible for the hands to be introduced into the danger zone of closing fixtures. by choosing the location of deadman’s controls so as to exclude the introduction of the hands into the danger zone or by providing a moving guard which has to be closed before the clamping movement can be started. To prevent chucks from running off the spindle when the lathe is suddenly braked. Safety engineering measures on the shop floor should be directed in particular at the following points: · work-holding fixtures (faceplates. and it must be impossible to start the spindle. It is important to provide for auxiliary lifting equipment to facilitate mounting and removing of heavy chucks and faceplates. The absence of power must not cause the opening or closure of a powered work-holding fixture. Removal of holding fixtures from the spindle should be possible only when the spindle has ceased rotating. The chuck keys in general should be so designed that it is impossible to leave them in the chuck. collets and tailstock centres. This can be achieved by putting a retaining nut with left-hand thread on the spindle nose. such as hydraulically operated chucks.Conduit and pipework should be installed in such a way that they do not become obstacles. they must be securely fixed. Bar feed weights must be guarded by hinged covers extending to the floor. by using a ―Camlock‖ quick-action coupling. collets) should be dynamically balanced before use · the maximum permissible speed of a chuck should be indicated on the chuck by the manufacturer and respected by the lathe operator · when scroll chucks are used. When powered work-holding fixtures are used. the machine should be equipped with a device which prevents the spindle rotation being started before the jaws are closed. This can be achieved by limiting the travel of the clamping element to 6 mm. Carriers .

. If special tool-setting operations are required. or a protective collar should be fitted to a conventional carrier. NC and CNC lathes should be completely enclosed. Working zone of the lathe Universal-lathe chucks should be guarded by hinged covers. In certain cases. the operator can be protected by special circuit designs (e. The working zones of semi-automatic.g. This can be achieved by using two-hand controls. by cutting the spindlemotor power supply). Ergonomics Every machine should be so designed that it enables a maximal output to be obtained with a minimum of stress on the operator. gauging and so on. protective covers should be interlocked with spindle drive circuits. The enclosures are generally sliding covers with limit switches and interlocking circuit. Enclosures of fully automatic machines should only have openings through which the stock to be machined is introduced. when filing work in a lathe—unprotected carriers must not be used. such as change of work or tools. Vertical boring and turning mills should be fenced with bars or plates to prevent injury from revolving parts. To enable the operator to watch the machining process safely. Turning swarf Long turning chips are dangerous because they may get entangled with arms and legs and cause serious injury. by permitting only one movement to be tripped at a time). The working zones of automatic lathes. platforms with railings must be provided. feeds and chip thicknesses or by using lathe tools with chip breakers of the gullet or step type. A centring safety carrier should be used. It is also possible to use self-locking carriers or to provide the carrier disc with a protective cover. TV cameras can be installed so that the operator may monitor the tool edge and tool in-feed. Zeroing a variable-speed drive is not considered a safe standstill. NC and CNC lathes must be enclosed during the machining process. Operations requiring access to the working zone. This can be achieved by adapting the machine to the worker. and it must be impossible to reach through them into the danger zone. . the turned part ejected and the swarf removed from the working zone. These openings must not constitute a hazard when work passes through them.g. Continuous and ravelled chips can be avoided by choosing appropriate cutting speeds. must not be carried out before the lathe has been safely stopped. Swarf hooks with handle and buckle should be used for removing chips. If possible. an inching control is to be provided which enables certain machine movements to be tripped while the protective cover is open. In such cases. Machines with such drives must have locked protective covers that cannot be unlocked before the machine is safely stopped (e.To prevent serious accidents—in particular..

If the operator has to work standing up. air movement and radiant heat. No finger rings and bracelets should be worn when working on lathes. checking adjustments and cleaning lathes. affording an adequate level of illumination. Measures should be taken to create optimal thermal comfort. Wearing of safety spectacles should be obligatory. correct choice and handling of tools should become routine to such an extent that the operator works correctly even if his or her concentration is temporarily relaxed. When heavy workpieces are machined. Training The lathe operator’s safety depends to a large extent on working methods. and the sleeves must be tightly buttoned at the wrists. Protective gloves must be worn whenever swarf is being collected. Important points in a training programme are an upright posture. All controls must be located within the physiological sphere or reach of both hands. sound-absorbent-lined guide tubes should be used. Maintenance . The workplace should preferably be provided with uniform lighting. Workers must be well informed about the hazards of injury which may be caused when gauging work. Belts should not be worn. correct movements. such as loading and unloading attachments. Work Clothing and Personal Protection Overalls should be close fitting and buttoned or zipped to the neck. When machining bar stock. There should be local exhaust devices to eliminate gaseous emanations. he or she should be given the possibility of changing posture. Experience has shown that good work is performed when the workplace is designed for both standing and sitting postures. Rational workplace design also includes providing for auxiliary handling equipment. The workshop should be adequately ventilated. Flexible seats are in many cases a welcome relief for strained feet and legs. safety shoes with steel toe caps must be worn. the proper mounting and removal of the chuck and the accurate and secure fixing of workpieces. They should be without breast pockets. Pedal-operated controls should be avoided in machines tended by standing operators. Correct posture.Ergonomic factors must be taken into account when designing the human-machine interface of a lathe. The controls must be clearly laid out and should be logical to operate. Correct holding of files and scrapers and safe working with abrasive cloth must be intensively practised. relative humidity. taking into account the air temperature. It is therefore important that he or she should receive thorough theoretical and practical training to acquire skills and develop a behaviour affording the best possible safeguards.

Grinding generally involves the use of a bonded abrasive to wear away parts of a workpiece. In grinding wheels and the like. Buffing does not remove metal. whetting and lapping. grinding segments. glass. especially for polishing and buffing. Buffing wheels are made from cotton or other textile disks sewn together. Aluminium oxide. tripoli. The natural abrasives—natural corundum or emery (aluminium oxides). files. The aim is to give the work a certain shape. sharpening stones.formaldehyde resin. silicon carbide (carborundum) and synthetic diamonds. tin putty and iron oxide are also used. Welinder* *Adapted from the 3rd edition. Aluminium oxide is most widely used in grinding wheels. Notable among organic bonding agents are phenol. removal of surface scale from metals before forging or welding and deburring of parts in sheet metal and machine shops.or urea. rubber and shellac. Faults must be corrected immediately. sandstone. A number of finegrained materials such as chalk. wood. stone. flint and garnet—have been largely superseded by artificial abrasives including aluminium oxide (fused alumina). belts. correct its dimensions. pumice. followed by silicon carbide. The tools used are wheels of varying dimensions. generally porous body. Encyclopaedia of Occupational Health and Safety. diamond. the machine should be put out of operation until corrective action has been taken. If safety is at stake in the event of a fault. The main type of inorganic bonds are vitrified silicate and magnesite. The vitrified bonding agents and phenolic resin are completely dominating within their respective groups. but uses a soft abrasive blended in a wax or grease base to produce a high-lustre surface. Both organic and inorganic bonding agents are used in grinding wheels. GRINDING AND POLISHING K. polishing wheels. such as polishing. discs and so on. In the case of abrasive belts. silicon carbide. The term covers other methods of producing very smooth and glossy surfaces. Natural and artificial diamonds are used for important special applications. pottery and so on. honing. emery. Grinding is the most comprehensive and diversified of all machining methods and is employed on many materials—predominantly iron and steel but also other metals. grinding points. the abrasive material is held together by bonding agents to form a rigid. increase the smoothness of a surface or improve the sharpness of cutting edges. garnet and flint are used in grinding and polishing belts. Examples include removal of sprues and rough edges from a foundry casting. the bonding agent holds the abrasive secured to a flexible base material. plastics. Polishing is used to remove surface imperfections such as tool marks.Lathes must be regularly maintained and lubricated. Diamond grinding . Repair and maintenance work must be carried out only after the machine has been isolated from the power supply.

For example. may incorporate glass fibre fabric at the centre or at each side. as well as different properties with regard to safety. In some countries. which takes no part in the grinding. are tougher than those with inorganic bonds and more resistant to impacts. often incorporate various types of reinforcement. The most common method of reinforcing grinding wheels. Wheels with organic bonds. grinding wheels operate at high speeds.wheels can also be metal bonded. Abrasive and polishing belts and discs are composed of a flexible base of paper or fabric to which the abrasive is bonded by means of a natural or synthetic adhesive. rough grinding and cutting. Common equipment types include: surface-type grinders. With the exception of some grinding wheels of small dimensions. Test regulations vary from country to country. such as surface grinding. Thin wheels. cylindrical (including centreless) grinding. and multiple polishers and buffers. however. billets and the like at speeds up to 80 m/s. abrasive cut-off machines. is to include glass fibre fabric in their construction. Large wheels with a centre section reinforced in this way are used particularly by the steel works for grinding slabs. High peripheral speeds may be permissible for wheels with organic bonds. but usually the wheel has to be tested at a speed 50% above the working speed. During rotation the major stress develops around the centre hole. such as those used for cutting. Hazards and Their Prevention Bursting The major injury risk in the use of grinding wheels is that the wheel may burst during grinding. can thus be made of an especially strong material which is not suitable for grinding. the nature of the bonding agent is most important. Different machines are used for different types of operations. The two main types are: those where either the grinder or the work is moved by hand and machines with mechanical feeds and chucks. while thicker wheels have a number of fabric layers depending on the thickness of the wheel. The various bonding agents give the wheels different grinding properties. belt polishers. polishers and buffers. To strengthen the wheel. internal grinders. pedestal-type grinders. portable grinders. There is a trend towards ever-increasing speeds. regulations require special testing of wheels that are to operate at . the section around the centre hole. Very high-speed wheels. in particular. Most industrialized nations have regulations limiting the maximum speeds at which the various types of grinding wheels may be run. Normally. polishers and buffers. In tests the wheels are run over a certain period at a speed exceeding that permitted in grinding. internal grinding. in particular phenolic resin. certain cup wheels are fitted with steel hubs to increase their strength. disk grinders and polishers. The fundamental protective measure is to make the grinding wheel as strong as possible. either all wheels or a statistical sampling of them must be given speed tests by the manufacturer.

catch and injure the operator’s hand. · Checking for cracks.higher speeds than normal at a central testing institute. · Work rest. which may result in bursting when the wheel is next used. it should be tested at full speed with due precautions being observed. A faultless vitrified wheel will give a clear ring. otherwise the water may collect at the bottom of the wheel and cause imbalance. Precautionary measures include: · Handling and storing. The spindle should be of adequate diameter but not so large as to expand the centre hole of the wheel. an organic bonded wheel a less ringing tone. A notice indicating the spindle speed should be fitted to all grinding machines. the wheel should be run idle to eject the water. occasional wheel bursts or breaks may still occur unless proper care is exercised in their use. The manufacturer is also obliged to ensure that the grinding wheel is well balanced prior to delivery. In spite of all precautions taken by the manufacturers. flanges should be not less than one-third the diameter of the wheel and made of mild steel or of similar material. more probable. Accidents and breakages occur when grinding wheels are mounted on unsuitable apparatus—for example. . Special precautions are necessary with variable speed grinding machines and to ensure the fitting of wheels of appropriate permissible speeds in portable grinders. Moisture may attack the bonding agent in phenolic resin wheels. bending tests and so on. but either can be differentiated from the cracked sound of a defective wheel. · Testing. Vitrified wheels may be sensitive to repeated temperature variations. most simply by tapping with a wooden mallet. Irregularly absorbed moisture may throw the wheel out of balance. · Mounting. Cutting wheels are subjected to certain impact tests. In no circumstances should the maximum permissible operating speed specified by the makers be exceeded. rigidly mounted work rests of adequate dimensions should be provided. In case of doubt. Wherever practicable. it is most important that wheels are carefully handled at all stages and kept in an orderly manner in a dry and protected place. · Speed. The bursting of a grinding wheel may cause fatal or very serious injuries to anyone in the vicinity and heavy damage to plant or premises. A wheel may become damaged or cracked during transit or handling. They should be adjustable and kept as close as possible to the wheel to prevent a trap in which the work might be forced against the wheel and break it or. on spindle ends of buffing machines. and the wheel should be marked with the maximum permissible peripheral speed and the corresponding number of revolutions for a new wheel. A new wheel should be checked to ensure that it is undamaged and dry. Before the new wheel is put into service. ultimately reducing their strength. Consequently. After wet grinding. the wheel should not be used and the supplier should be consulted. The institute may also cut specimens from the wheel and investigate their physical properties.

grains and splinters are a common hazard to the eyes in all dry-grinding operations. Figure 82. The spindles and tapered ends of double-ended polishing machines can cause entanglement accidents unless they are effectively guarded. and an adjustable nose piece may be necessary. the volume of dust produced by grinding makes efficient LEV essential. for tool grinding. cast iron and cast aluminium are to be avoided. where the nature of the work precludes the use of a guard. It is more difficult to provide local exhaust for portable wheels. Health hazards Although modern grinding wheels do not themselves create the serious silicosis hazard associated in the past with sandstone wheels. Vibration Portable and pedestal grinders carry a risk of hand-arm vibration syndrome (HAVS).5). Certain resin-bonded wheels may contain fillers which create a dangerous dust. redesigning tools. highly dangerous silica dust may still be given off from the materials being ground—for example. fixed eye shields are particularly useful when wheels are in intermittent use—for example. Abrasive wheels should be provided with guards strong enough to contain the parts of a bursting wheel (see figure 82. high-velocity capture systems. although some success in this direction has been achieved by use of low-volume.5 A well guarded.· Guarding. abrasives. Effective eye protection by goggles or spectacles and fixed eye shields at the machine are essential. Prolonged work should be avoided and respiratory protective equipment provided if . Some countries have detailed regulations regarding the design of the guards and the materials to be used. In addition. In general. sand castings. In any event. special protective flanges or safety chucks may be used. Recommendations include limiting intensity and duration of exposure. Textile dust released from buffing operations is a fire hazard requiring good housekeeping and LEV. also known as ―white finger‖ from its most noticeable sign. protective equipment and monitoring exposure and health. Fire Grinding of magnesium alloys carries a high fire risk unless strict precautions are taken against accidental ignition and in the removal and drenching of dust. Exceptionally. The grinding opening should be as small as possible. vitrified abrasive wheel mounted in a surface grinder and operating at a peripheral speed of 33 m/s Eye injuries Dust. High standards of cleanliness and maintenance are required in all exhaust ducting to prevent risk of fire and also to keep ventilation working efficiently. formaldehyde-based resins can emit formaldehyde during grinding.

or where it is difficult and expensive to re-apply the lubricant. the requirements for lubricants and metal process oils become more stringent. Industrial Oils Industrial oils such as spindle and lubricating oils. such as in aerospace applications. Lubricating oils now range from clear. With buffing in particular. Lubricants for aerospace use must meet entirely new conditions. combustible textile dust is a serious concern.necessary. to thick. hydraulic and turbine oils and transmission fluids are designed to meet specific physical and chemical requirements and to operate without discernible change for extended periods under varying conditions. where the increased time between oil changes offsets the difference in cost. very thin oils used to lubricate delicate instruments. Oils with very specific requirements are used both in the hydraulic systems and to lubricate large computer-operated machine tools such as those used in the aerospace industry to produce parts with extremely close tolerances. Exhaust ventilation is also required for most belt sanding. and blends of synthetic and petroleum-based oils. industry depended on naturally occurring oils and animal fats such as lard and whale sperm oil for lubricating moving parts. such as sealed-for-life electric motors. to modern synthetic oils and greases with longer service life. fluids and greases. especially for metal grinders. including cleanliness. durability. INDUSTRIAL LUBRICANTS. polishing and similar operations. which are used in parts such as small electrical motor bearings. Industrial Lubricants All moving parts on machinery and equipment require lubrication. gear lubricants. cutting oils and greases. and medical supervision is desirable. Although lubrication may be provided by dry materials such as Teflon or graphite. tar-like oils used on large gears such as those which turn steel mills. where extended temperature and pressure ranges exist. finishing. These oils and animal products were especially susceptible to melting. superior lubricating qualities and better resistance to change under varying temperatures and climatic conditions. The evolution of petroleum-based refined products has continued from the first lubricant. Protective clothing and good sanitary and washing facilities with showers should be provided. are used where extended lubricant life is desired. oils and greases are the most commonly used lubricants. oxidation and breakdown from exposure to heat and moisture produced by the steam engines which powered almost all industrial equipment at that time. Kraus The industrial revolution could not have occurred without the development of refined petroleumbased industrial oils. METAL WORKING FLUIDS AND AUTOMOTIVE OILS Richard S. Prior to the discovery in the 1860s that a superior lubricant could be produced by distilling crude oil in a vacuum. Synthetic oils. resistance to . which was used to tan leather. lubricants. As the complexity of the machinery increases.

Spindle oils are thin. high lubricity. The characteristics of gear oils include good chemical stability. have a high viscosity index and resist water wash (steam-operated cylinders) and detergency. provide a seal to resist blowback pressure. rust protection and good demulsibility. have established specific performance criteria for automotive engine oils. thermal stability.cosmic radiation and the ability to operate in extremely cold and hot temperatures. Automotive Engine Oils Manufacturers of internal combustion engines and organizations. piping. Internal combustion engine oils must not be too thick to lubricate the internal moving parts when an engine starts up in cold weather. wear protection. transmissions and gear cases are designed with high viscosity indexes to resist changes in viscosity with temperature changes. provide lubrication for cylinders and pistons. turbines and hydraulic systems contain fluids which transfer force or power. such as the Society of Automotive Engineers (SAE) in the United States and Canada. coolers and filters. transmissions and turbines require fluids with specific viscosities and chemical stability to operate smoothly and provide the controlled transfer of power. and they must not thin out as the engine heats up when operating. Cylinder and compressor oils combine the characteristics of both industrial and automotive oils. Oils for automotive engines. detergency and high and low temperature performance. Gear lubricants are designed to form strong. tenacious films which provide lubrication between gears under extreme pressure. act as a heat transfer agent (internal combustion engine cylinders). Automotive engine oils contain detergents designed to hold carbon and metallic wear particles in suspension so that they can be filtered out as the oil circulates and not accumulate on internal engine parts and cause damage. demulsibility and resistance to viscosity increase and deposit formation. corrosion resistance. without gravity and in a vacuum. extremely clean and clear oils with lubricity additives. Cutting Fluids . They should resist carbon build-up on valves. reservoirs to hold the fluids. lubricity. have chemical and thermal stability (especially vacuum pump oil). Automotive gasoline and diesel engine oils are subjected to a series of performance tests to determine their chemical and thermal stability. Transmissions. anti-foam capabilities. pumps to move the fluids from one place to another and auxiliary equipment such as valves. long life in circulating systems. Automotive engine oils are especially formulated to resist breakdown under heat as they lubricate internal combustion engines. viscosity. deposit resistance. They are then classified according to a code system which allows consumers to determine their suitability for heavy-duty use and for different temperatures and viscosity ranges. Hydraulic systems. rings and cylinders and the formation of corrosive acids or deposits from moisture. The most important characteristics for way oils—used to lubricate two flat sliding surfaces where there is high pressure and slow speed—are lubricity and tackiness to resist squeezing out and resistance to extreme pressure. They should resist accumulation of deposits. The characteristics of good hydraulic and turbine oils include a high viscosity index.

A gapped or multi-phase quenching oil is used to treat high carbon and alloy steels. automatic screw machines. Soluble water-in-oil cutting fluids are mineral oils (or synthetic oils) which contain emulsifiers and special additives including defoamants. the cutting tool being used and the type of cutting. inexpensive steel parts. preventing gummy deposits upon evaporation and a safe flashpoint for the work performed. Synthetic cutting fluids are solutions of non-petroleum-based fluids. Quenching in lighter oil is used to case harden small. rust inhibitors. copper and brass. oxidation stability and high flashpoint. Release oils are used to coat dies and moulds to facilitate the release of the formed metal parts. is provided by synthetic and animal fats or sulphurized sperm oil additives. Cutting fluids improve and enhance the metal working process by cooling and lubrication (i. additives and water. . The desired characteristics of cutting fluids depend on the composition of the metal being worked on. planing or shaping operation performed. Lubricity. They are diluted with water in varying ratios before being used. Transformer oils are specially formulated dielectric fluids used in transformers and large electric breakers and switches.. as it goes through hot and cold rolling mills. Semi-synthetic fluids contain 10 to 15% mineral oil.e.The three types of cutting fluids used in industry are mineral oils. Roll oils are specially formulated mineral or soluble oils which lubricate and provide a smooth finish to metal. Quench oils. detergents. Their characteristics include thermal and chemical stability. Heat transfer oils are used in open or closed systems and may last up to 15 years in service. when working on a soft metal which creates a lot of heat. chlorine or phosphorus compounds. soluble oils and synthetic fluids. are used in metal treating to control the change of the molecular structure of steel as it cools. protecting the edge of the cutting tool). For example. rather than emulsions. Some special fluids have both lubricating oil and cutting fluid characteristics due to the tendency of fluids to leak and intermix in certain machine tools such as multi-spindle. cooling is the most important criterion. which is important when working on steel to overcome the abrasiveness of iron sulphide. Other Metal Working and Process Oils Grinding fluids are designed to provide cooling and prevent metal build-up on grinding wheels. some of which are fire resistant for machining specific metals. Tanning oils are still used in the felt and leather-making industry. A slower quench rate is used to produce machine tool steels which are fairly hard on the outside with lower internal stress. Control of the builtup edge on cutting tools is provided by anti-weld or anti-wear additives such as sulphur. high-stability mineral oils of various viscosities together with additives to provide specific characteristics depending on the type of material being machined and the work performed. particularly aluminium. Cutting oils are typically a blend of high-quality. which require high stability. Heat transfer oils are normally too viscous to be pumped at ambient temperatures and must be heated to provide fluidity. bactericides and germicides. The primary characteristics are good thermal stability as systems operate at temperatures from 150 to 315°C. Improved cooling is provided by using a light oil (such as kerosene) or water-based cutting fluid. rust protection (soluble fluids).

Rust preventive oils may be either solvent or water based. and resisting acid or water washout.g. lead naphthenate or zinc dithiophosphate. sodium. paracresol and phenyl naphthylamine. which are hard to reach or where leaking or splashed liquid lubricants might contaminate products or create a hazard. Grease is made by the blending of metallic soaps (salts of long-chained fatty acids) into a lubricating oil medium at temperatures of 205 to 315°C. Grease and Automotive Engine Oil Additives In addition to using high-quality lubricant base stocks with chemical and thermal stability and high viscosity indexes.Petroleum solvents are used to clean parts by spraying. reduce the rate of deterioration of oil by breaking up the long-chain molecules which form when exposed to oxygen. fatty acids for added lubricity. in order to maintain constant hydraulic pressure and prevent cavitation. bearings and other parts by dipping or spraying. metallic element (e. · Foam inhibitors. thickeners and additives used to lubricate parts and equipment which cannot be made oil-tight. Industrial Lubricants. lithium and so on) in the soap and the additives used to improve performance and stability and to reduce friction. such as 2. and leave polarized or wax films on the metal surfaces for fingerprint and rust protection and water displacement. greases and automotive engine oils. They are applied to stainless steel coils. gear oils.6-ditertiary butyl. Synthetic greases may use di-esters. aluminium. Defoamants. colour dyes for identification and water inhibitors. transmission fluids and turbine oils to reduce surface film tension and remove air entrapped in the oil by pumps and compressors. such as silicones and polyorganic silioxanes. Greases Greases are mixtures of fluids. The most commonly used additives include but are not limited to the following: · Anti-oxidants. Some greases may contain graphite or molybdenum fillers which coat the metallic parts and provide lubrication after the grease has run out or decomposed. Oxidation inhibitors are used to coat metals such as copper. dripping or dipping. tackiness additives. anti-oxidants. These additives include extreme-pressure additives which coat the metal with a thin layer of non-corrosive metallic sulphur compounds. Oxidation inhibitors. as well as the continuous friction created by railroad car wheel roller bearings. are used in hydraulic oils. rust inhibitors. from lubricating jet engine bearings at sub-zero temperatures to hot rolling mill gears. . The characteristics of the grease depend to a great extent upon the particular fluid. cutting fluids. silicone or phosphoric esters and polyalkyl glycols as fluids. calcium.. speeding up oxidation and forming acids which attack other metals. additives are needed to enhance the fluid and provide specific characteristics required in industrial lubricants. zinc and lead to prevent contact with the oil so they will not act as catalysts. They have a wide range of applications and performance requirements. The solvents remove oil and emulsify dirt and metal particles.

Extreme pressure additives. gear and transmission oils to form coatings which protect metal surfaces when the protective oil film thins or is squeezed out and cannot prevent metal to metal contact. Fat. · Emulsifiers. Water inhibitors and special compounds separate water out of oil and prevent gum formation. Dyes are used to assist users to identify different oils used for specific purposes. air compressors and gear cases contaminated by soluble cutting fluids. Anti-rust additives. reduce odours and prevent dermatitis. Bactericides and germicides. their effectiveness diminishes with extended use. Metal sulphonate and metal phenate detergents are used to hold dirt. form polar compounds which are attracted to metal surfaces and provide a physical layer of additional protection in the event that the oil film is not sufficient. . zinc dithiophosphate and lead naphthenate. such as phenol and pine oil. gear cases. · Anti-wear additives. · Extreme pressure additives. · Tackiness additives. lard. · Viscosity index improvers. and overhead machinery. gear oils. allowing them to maintain their structure over wider temperature ranges and for much longer periods of time than mineral oils with viscosity index improver additives. · Demulsifiers. such as transmission fluids and gear oils. Adhesive or tackiness additives are used to enable oils to adhere to and resist leakage from bearing assemblies.· Corrosion inhibitors. are added to soluble cutting oils to prolong the life of the fluid. large open gears on mills and construction equipment. · Lubricity additives. · Colour dyes. engine oils and transmission fluids. sperm and vegetable oils are used to provide a higher degree of oiliness in cutting oils and some gear oils. Unfortunately. They are used where equipment is subject to water wash or where a large amount of moisture is present. tallow. · Detergents. they contain waxy oils which provide added lubricity. such as tricresylphosphate. · Bactericides. Synthetic oils are designed with very high viscosity indexes. maintain stability. in order to prevent misapplication. such as non-corrosive sulphurized fatty compounds. are used in automotive. Viscosity index improvers help oils resist the effects of temperature changes. Anti-wear additives. such as lead naphthenate and sodium sulphonate. are used to prevent rust from forming on metallic parts and systems where circulating oil has been contaminated with water or by moist air which entered system reservoirs as they cooled down when the equipment or machinery was not in use. such as in steam cylinders. These contaminants are typically removed when the oil passes through a filter to prevent their being recirculated through the system where they could cause damage. Their tackiness diminishes with extended service. carbon and metallic wear particles in suspension in hydraulic oils. Fatty acids and fatty oils are used as emulsifiers in soluble oils to help form solutions with water.

Manufacturing Industrial Lubricants and Automotive Oils
Industrial lubricants and oils, grease, cutting fluids and automotive engine oils are manufactured in blending and packaging facilities, also called ―lube plants‖ or ―blending plants‖. These facilities may be located either in or adjacent to refineries which produce lubricant base stocks, or they may be some distance away and receive the base stocks by marine tankers or barges, railroad tank cars or tank trucks. Blending and packaging plants blend and compound additives into lubricating oil base stocks to manufacture a wide range of finished products, which are then shipped in bulk or in containers. The blending and compounding processes used to manufacture lubricants, fluids and greases depend on the age and sophistication of the facility, the equipment available, the types and formulation of the additives used and the variety and volume of products produced. Blending may require only physical mixing of base stocks and additive packages in a kettle using mixers, paddles or air agitation, or auxiliary heat from electric or steam coils may be needed to help dissolve and blend in the additives. Other industrial fluids and lubricants are produced automatically by mixing base stocks and pre-blended additive and oil slurries through manifold systems. Grease may be either batch produced or continuously compounded. Lube plants may compound their own additives from chemicals or purchase pre-packaged additives from specialty companies; a single plant may use both methods. When lube plants manufacture their own additives and additive packages, there may be a need for high temperatures and pressures in addition to chemical reactions and physical agitation to compound the chemicals and materials. After production, fluids and lubricants may be held in the blending kettles or placed in holding tanks to ensure that the additives remain in suspension or solution, to allow time for testing to determine whether the product meets quality specifications and certification requirements, and to allow process temperatures to return to ambient levels before products are packaged and shipped. When testing is completed, finished products are released for bulk shipment or packaging into containers. Finished products are shipped in bulk in railroad tank cars or in tank trucks directly to consumers, distributors or outside packaging plants. Finished products also are shipped to consumers and distributors in railroad box cars or package delivery trucks in a variety of containers, as follows: · Metal, plastic and combination metal/plastic or plastic/fibre intermediate bulk containers, which range in size from 227 l to approximately 2,840 l, are shipped as individual units on builtin or separate pallets, stacked 1 or 2 high. · Metal, fibre or plastic drums with a capacity of 208 l, 114 l or 180 kg are typically shipped 4 to a pallet. · Metal or plastic drums with a capacity of 60 l or 54 kg, and 19 l or 16 kg metal or plastic pails, are stacked on pallets and banded or stretch wrapped to maintain stability.

· Metal or plastic containers with a capacity of 8 l or 4 l, 1 l plastic, metal and fibre bottles and cans and 2 kg grease cartridges are packaged in cartons which are stacked on pallets and banded or stretch wrapped for shipment. Some blending and packaging plants may ship pallets of mixed products and mixed sizes of containers and packages directly to small consumers. For example, a single-pallet shipment to a service station could include 1 drum of transmission fluid, 2 kegs of grease, 8 cases of automotive engine oil and 4 pails of gear lubricant.

Product Quality
Lubricant product quality is important to keep machines and equipment operating properly and to produce quality parts and materials. Blending and packaging plants manufacture finished petroleum products to strict specifications and quality requirements. Users should maintain the level of quality by establishing safe practices for the handling, storage, dispensing and transfer of lubricants from their original containers or tanks to the dispensing equipment and to the point of application on the machine or equipment to be lubricated or the system to be filled. Some industrial facilities have installed centralized dispensing, lubrication and hydraulic systems which minimize contamination and exposure. Industrial oils, lubricants, cutting oils and grease will deteriorate from water or moisture contamination, exposure to excessively high or low temperatures, inadvertent mixing with other products and long-term storage which allows additive drop-out or chemical changes to occur.

Health and Safety
Because they are used and handled by consumers, finished industrial and automotive products must be relatively free of hazards. There is a potential for hazardous exposures when blending and compounding products, when handling additives, when using cutting fluids and when operating oil mist lubrication systems. The chapter Oil and natural gas refineries in this Encyclopaedia gives information regarding potential hazards associated with auxiliary facilities at blending and packaging plants such as boiler rooms, laboratories, offices, oil-water separators and waste treatment facilities, marine docks, tank storage, warehouse operations, railroad tank car and tank truck loading racks and railroad box car and package truck loading and unloading facilities. Safety Manufacturing additives and slurries, batch compounding, batch blending and in-line blending operations require strict controls to maintain desired product quality and, along with the use of PPE, to minimize exposure to potentially hazardous chemicals and materials as well as contact with hot surfaces and steam. Additive drums and containers should be stored safely and kept tightly sealed until ready for use. Additives in drums and bags need to be handled properly to avoid muscular strain. Hazardous chemicals should be properly stored, and incompatible chemicals should not be stored where they can mix with one another. Precautions to be taken when operating filling and packaging machinery include using gloves and avoiding catching

fingers in devices which crimp covers on kegs and pails. Machine guards and protective systems should not be removed, disconnected or by-passed to expedite work. Intermediate bulk containers and drums should be inspected before filling to make sure they are clean and suitable. A confined-space permit system should be established for entry into storage tanks and blending kettles for cleaning, inspection, maintenance or repair. A lockout/tagout procedure should be established and implemented before working on packaging machinery, blending kettles with mixers, conveyors, palletizers and other equipment with moving parts. Leaking drums and containers should be removed from the storage area and spills cleaned up to prevent slips and falls. Recycling, burning and disposal of waste, spilled and used lubricants, automotive engine oils and cutting fluids should be in accordance with government regulations and company procedures. Workers should use appropriate PPE when cleaning spills and handling used or waste products. Drained motor oil, cutting fluids or industrial lubricants which may be contaminated with gasoline and flammable solvents should be stored in a safe place away from sources of ignition, until proper disposal. Fire protection While the potential for fire is less in industrial and automotive lubricant blending and compounding than in refining processes, care must be taken when manufacturing metal working oils and greases due to the use of high blending and compounding temperatures and lower flashpoint products. Special precautions should be taken to prevent fires when products are dispensed or containers filled at temperatures above their flashpoints. When transferring flammable liquids from one container to another, proper bonding and grounding techniques should be applied to prevent static build-up and electrostatic discharge. Electrical motors and portable equipment should be properly classified for the hazards present in the area in which they are installed or used. The potential for fire exists if a leaking product or vapour release in the lube blending and grease processing or storage areas reaches a source of ignition. The establishment and implementation of a hot-work permit system should be considered to prevent fires in blending and packaging facilities. Storage tanks installed inside buildings should be constructed, vented and protected in accordance with government requirements and company policy. Products stored on racks and in piles should not block fire protection systems, fire doors or exit routes. Storage of finished products, both in bulk and in containers and packages, should be in accordance with recognized practices and fire prevention regulations. For example, flammable liquids and additives which are in solutions of flammable liquids may be stored in outside buildings or separate, specially designed inside or attached storage rooms. Many additives are stored in warm rooms (38 to 65°C) or in hot rooms (over 65°C) in order to keep the ingredients in suspension, to reduce the viscosity of thicker products or to provide for easier blending or compounding. These storage rooms should comply with electrical classification, drainage, ventilation and explosion venting requirements, especially when flammable liquids or combustible liquids are stored and dispensed at temperatures above their flashpoints.

Contact dermatitis may occur when employees are exposed to cutting fluids during production. Health hazards due to microbial contamination of oil may be summarized as follows: · Pre-existing skin conditions may be aggravated.Health When blending. leading to folliculitis. sampling and compounding. which can be controlled through the use of PPE and good personal hygiene practices. chemicals and additives. fumes. work or maintenance and when they wipe oil-covered hands with rags embedded with minute metal particles. · Head protection may be needed when working in pits or areas where the potential exists for injury to the head. vapours. · Safety goggles and respiratory protection may be needed for hazardous exposures to chemicals. · Impervious gloves. birds or humans may be introduced. · Harmful bacteria from animals. solvents and spindle oils defat the skin and cause rashes. and . and approved protective toe safety shoes with oil. Thicker products. block the pores of the skin.or slip-resistant soles should be worn for general work. fumes and vapours. additives and caustic solutions and when cleaning up spills. noise and heat when conducting inspection and maintenance activities while sampling and handling hydrocarbons and additives during the production and packaging and when cleaning up spills and releases: · Work shoes with oil. good hygiene and appropriate personal protection may be needed for exposure to oil mists. such as gear oils and greases. dust or steam. Lighter oils such as kerosene. face shields and chemical goggles should be worn when handling hazardous chemicals. mists. Safe work practices. Oil is a common cause of dermatitis. metallic salts. The metal causes small lacerations in the skin which may become infected. additives. · Organisms may change the composition of the product so that it becomes directly injurious. · Lubricant aerosols of respirable size may cause respiratory illness. Direct skin contact with any formulated greases or lubricants should be avoided. steam.or slip-resistant soles should be worn where hazards of foot injuries from rolling or falling objects or equipment exist. aprons. footwear. · Ready access to appropriate cleaning and drying facilities to handle splashes and spills should be provided. personal and respiratory protective equipment should be considered to prevent exposures to heat. Water-based cutting fluids on skin and clothing may contain bacteria and cause infections. dusts.

M. asthma. Employees should remove and launder clothing that is soaked with oil before wearing it again. Morse. cause irritation of the skin and may be potentially hazardous. as well as the additives in their formulations. Exposures to chlorinated compounds and leaded compounds. Manufacturers should have material safety data sheets (MSDSs) or other product information available for all of the additives and base stocks used in blending and compounding. Encyclopaedia of Occupational Health and Safety. oils and greases. Oil folliculitis is caused by prolonged exposure to oil-based cutting fluids. J. chronic bronchitis and impaired pulmonary function (NIOSH 1996). Metal working fluids are readily contaminated by bacteria and fungi. J. N. They may affect the skin or. they may have systemic effects.R. The specific formulations responsible for the elevated cancer risks remain to be determined. Commercial triethanolamine contains diethanolamine. Jones. Dermatitis may also be caused by using soaps. Occupational exposure to oil mists and aerosols is associated with a variety of non-malignant respiratory effects. G. Thomas. Catton. El Kadeem and Philip A. Bevan. acute airways irritation. Additives introduced in blending and compounding may also create a potential risk to health. Refinery processes such as hydrofinishing and acid treatment are used to remove aromatics from industrial lubricants. Medical advice should be sought when dermatitis persists. Synthetic oils consist mainly of sodium nitrite and triethanolamine and additives. including the stomach. Fish. larynx and rectum (NIOSH 1996). M. pancreas. Product safety information is important to employees of both manufacturers and users of lubricants.the emulsifiers may dissolve fats from the skin. the US National Institute for Occupational Safety and Health (NIOSH) found an association between exposure to metal working fluids and the risk of developing cancer at several organ sites. N-nitrosodiethanolamine. Zober. detergents or solvents to clean the skin. including lipoid pneumonia. such as from wearing oil-soaked clothing. Tri-orthocresyl phosphate has caused outbreaks of nerve palsies when lubricating oil was accidentally used for cooking. Semi-synthetic lubricants present the hazards of both products. SURFACE TREATMENT OF METALS J. Many companies have conducted epidemiological and toxicological testing to determine the degree of hazards associated with any acute and chronic health effects of their products. such as those used in some gear lubricants and greases. A.G. In the extensive review conducted as a basis for its criteria document. when inhaled as contaminated aerosols.A. Dermatitis is best controlled by good hygiene practices and minimizing exposure. Platcow* *Adapted from the 3rd edition. K.A. . which may create a hazard. and the use of naphthenic base stocks has been restricted in order to minimize carcinogenicity. which can react with sodium nitrite to form a relatively weak carcinogen. This information should be available to workers and users through warning labels and product safety information.

Install effective exhaust ventilation. Install proper machine guards. Install effective exhaust ventilation. HEPA-filtered equipment may be necessary. burns and irritation from caustic and corrosive Precautions Use appropriate personal protective equipment. electric shock. Install effective exhaust ventilation to avoid dust exposure. potential lead exposure Burn hazard from high temperature liquids. push-pull system. often slotted. causing slip and fall hazards. Implement a programme to avoid exposure to hydrofluoric acid. Use appropriate personal protective equipment. fit better and look better (see table 82. Use appropriate personal protective equipment. Install non-skid flooring. ergonomic hazards Physical hazards from grinders. This article will briefly describe some of those most commonly used. conveyers. Table 82. potential explosive dust generation. and equipment. Install effective exhaust ventilation. burns and irritation from caustic and corrosive chemicals. metal fume fever.7 Summary of the hazards associated with the different metal treatment methods Metal treatment method Electrolytic polishing Electroplating Hazards Burns and irritation from caustic and corrosive chemicals Exposure to potentially cancer causing chromium and nickel.There is a wide variety of techniques for finishing the surfaces of metal products so that they resist corrosion.7). Use appropriate personal protective equipment. Implement a lead exposure reduction/monitoring programme. Install effective exhaust ventilation. mills. burns and irritation from caustic and corrosive chemicals. metals. exposure to cyanides. including interlocks. exposure to dusts that may cause lung disease Exposure to hydrofluoric acid. Use effective design of work procedures and stations to avoid ergonomic stress. the process can be wet. burn hazard from high temperature liquids and equipment Burn hazard from high temperature liquids. Display signs warning of high temperature equipment and Enamels and glazing Etching Galvanizing Heat treatment . burn hazard from high temperature liquids and equipment. Use appropriate personal protective equipment. Clean up spills immediately. burns and irritation from caustic and corrosive chemicals. Some products are treated by a sequence of several of these techniques. metals and equipment. Use appropriate personal protective equipment. Install effective exhaust ventilation.

vapour degreasing. Install adequate fire suppression systems. Treatment Processes .chemicals. Install effective exhaust ventilation. Workers exposed to the hazard of splashes must be provided with protective goggles or eye shields and protective gloves. individually or in sequence. Use appropriate personal protective equipment. A number of methods of cleaning are used. Use appropriate personal protective equipment. brushing and polishing (which produce metallic or oxidic dust—aluminium dust may be explosive). and other standard electrical precautions. resulting in ―blank‖ metal surfaces that are free from oxides and grease. Showers and eyewash fountains should be nearby and in good working order. Seek alternatives to sensitizers. exposure to chemical sensitizers. exposure to potentially carcinogenic chromium Before any of these techniques can be applied. and splashes and spills should be washed away promptly. washing with organic grease solvents. Proper design of the equipment and effective LEV will reduce some of the risk. Properly separate chemicals/gases. Properly separate chemicals and gases. potential exposure to cyanides. potential exposure to carbon monoxide. Use appropriate personal protective equipment. Install systems to monitor the concentration of carbon monoxide. fire hazard from oil quenching Metallizing Burn hazard from high temperature metals and equipment. Install effective exhaust ventilation. With electrolytic equipment. Use appropriate personal protective equipment. ―pickling‖ in concentrated acid or alkaline solutions and electrolytic degreasing. Seek alternatives to sensitizers. The last involves immersion in baths containing cyanide and concentrated alkali in which electrolytically formed hydrogen or oxygen remove the grease. such as the installation of ground fault circuit interrupters and lockout/tagout procedures should be followed. The cleaning is followed by adequate rinsing and drying of the product. Install effective exhaust ventilation. the products must be thoroughly cleaned. acetylene. the gloves and shoes must be non-conducting. They include mechanical grinding. possible explosive atmospheres of hydrogen. Install adequate firesuppression systems. aprons and clothing. possible explosive atmospheres of dust. Install effective exhaust ventilation. Phosphating Plastics coating Priming Exposure to various solvents which are potentially toxic and flammable. zinc metal fume fever Burns and irritation from caustic and corrosive chemicals Exposure to chemical sensitizers surfaces.

a process closely related to electroplating.. instead of the formation of positive aluminium ions and migrating for deposition on the cathode. hard chromium to improve the surface properties or silver and gold to beautify it. for example.→ Cu In electroforming. they are oxidized by the oxygen atoms arising at the anode and become bound to it as an oxide layer. where they are reduced to the metal and deposited as a thin layer (see figure 82. usually iron or steel. Occasionally. storage tanks and containers. wired as the cathode. Acids are frequently used as the electrolyte solutions. Enamels and glazes Vitreous enamel or porcelain enamel is used to give a high heat-. nickel to protect against corrosion. and an anode of the metal to be deposited are immersed in an electrolyte solution (which can be acidic. non-metallic materials are used.and corrosion-resistant covering to metals. in a wide range of fabricated products including bath tubs. and the product is then washed. Cathode: Cu2+ + 2e. enamels are used in the decoration of ceramics. making the surface layer porous. for example. products of aluminium (titanium and other metals are also used) are connected as the anode and immersed in dilute sulphuric acid. Subsequently. coloured or lightsensitive materials can be deposited in these pores. gas and electric cookers. glass. to remove excess metal to accurately fit the required dimensions and to prepare the surface for inspection for imperfections. In addition. dried and polished.6). This oxide layer is partially dissolved by the sulphuric acid solution. a process that has become increasingly important in recent years. The product. However. The positively charged cations of the metallic anode migrate to the cathode.6 Schematic representation of electroplating In anodization. accordingly. and electrical equipment. Electroplating Electroplating is a chemical or electrochemical process for applying a metallic layer to the product—for example. stain. jewellery and decorative ornaments. The process is continued until the new coating reaches the desired thickness.Electrolytic polishing Electrolytic polishing is used to produce a surface of improved appearance and reflectivity. plaster or plastic are made conductive by the application of graphite and then are connected as the cathode so that the metal is deposited on them. The process involves preferential anodic dissolution of high spots on the surface after vapour degreasing and hot alkaline cleaning. as in the fabrication of nameplates. alkaline or alkaline with cyanide salts and complexes) and connected externally to a source of direct current. adequate rinsing is required afterwards. objects moulded of. The specialized use of enamel powders in the production of such . Anode: Cu → Cu+2 + 2e. kitchen ware. Figure 82.

iron. vanadium. nickel. Although some dipping operations are being mechanized. barium carbonate. The first step in all types of vitreous enamelling or glazing is the making of the frit. in ―slushing‖. the enamel slip is thicker and must be shaken from the object. smelting and frit handing. uranium and titanium · opacifiers. the enamel powder. This involves preparation of the raw materials. . magnesium carbonate. such as borax. such as borax (sodium borate decahydrate). it melts down to a smooth surface. sodium nitrate. when the object is returned to the furnace. such as oxides of antimony.ornamental ware as Cloisonné and Limoges has been known for centuries. usually in a mechanized operation. titanium. lead tetroxide and zinc oxide · colours. sodium nitrite and sodium aluminate · flocculating agents.g. the ground-coated object is heated to the enamelling temperature and then dry enamel powder is dusted through sieves onto it. selenium. manganese. The materials used in the manufacture of vitreous enamels and glazes include: · refractories. such as quartz. fluorspar. shot blasting. After careful cleaning of the metal products (e. gums. Glazes are applied to pottery ware of all kinds. which usually is gas fuelled. and sodium antimoninate · electrolytes. such as oxides of antimony. cryolite.. bentonite and colloidal silica. It requires a cabinet under exhaust ventilation. ammonium alginate. such as clay. · Spray application is being used increasingly. · In the dry process. The enamel sinters into place and. degreasing). cobalt. the glaze is removed by a flick of the wrist and the object is placed in a dryer. The prepared objects are then ―fired‖ in a furnace or kiln. tin and zirconium. using brushes or similar tools. feldspar and clay · fluxes. soda ash (anhydrous sodium carbonate). the enamel may be applied by a number of procedures: · In the wet process. · Glazes for porcelain and pottery articles are usually applied by dipping or spraying. withdrawn and allowed to drain or. dipped into a large tub of glaze. pieces are usually dipped by hand in the domestic porcelain industry. the object is dipped into the aqueous enamel slip. cadmium. lead monoxide. soda ash. · Decorative enamels are usually applied by hand. magnesium carbonate and sulphate. pickling. The object is held in the hand. An enclosed hood or cabinet with efficient exhaust ventilation should be provided when the glaze is sprayed.

A typical acid treatment involves immersions of 15 to 60 seconds in a mixture of 3 parts by volume of nitric acid and 1 part by volume of hydrofluoric acid that is maintained at a temperature of 20°C. eliminating the flux and preheating in a reducing gas (e. Galvanizing Galvanizing applies a zinc coating to a variety of steel products to protect against corrosion. the pipe is immersed in a hot solution of zinc ammonium chloride after cleaning and before the pipe enters the molten zinc bath. The product must be clean and oxide-free for the coating to adhere properly. ―cold‖ galvanizing is essentially electroplating. In ―hot dip‖ galvanizing. The fluxes decompose to form irritating hydrogen chloride and ammonia gas. chromic or sulphuric acid. sheet or wire.. drying or annealing processes before the product enters the galvanizing bath. using a flux prior to the preheat furnace and annealing in a furnace before galvanizing · cleaning by acid pickling and alkali cleaning. but is also used for many other metals. it is used as a pre-treatment prior to anodizing. hydrogen) prior to galvanizing. The alkaline etching is usually preceded and followed by treatment in various mixtures of hydrochloric. nitric. Manufactured products are usually galvanized in a batch process. This usually involves a number of cleaning. A prefluxing step may be followed by an ammonium chloride flux cover on the surface of the zinc bath. . rinsing. the product is passed through a bath of molten zinc. The various types of continuous hot-dip galvanizing differ essentially in how the product is cleaned and whether the cleaning is done on-line: · cleaning by flame oxidation of the surface oils with subsequent reduction in the furnace and annealing done in-line · electrolytic cleaning done prior to in-line annealing · cleaning by acid pickling and alkali cleaning. as described above. Flux may be employed to maintain satisfactory cleaning of both the product and the zinc bath and to facilitate drying.Etching Chemical etching produces a satin or matte finish. hydrofluoric. phosphoric. conversion coating. together with other ingredients to prevent sludge formation. Most frequently.g. while the continuous strip method is used for steel strip. In galvanizing pipe. potassium hydroxide. lacquering. requiring LEV. or the latter may be used alone. trisodium phosphate and sodium carbonate. It is most frequently applied to aluminium and stainless steel. Aluminium is usually etched in alkaline solutions containing various mixtures of sodium hydroxide. One of the most common processes uses sodium hydroxide at a concentration of 10 to 40 g/l maintained at a temperature of 50 to 85°C with an immersion time as long as 10 minutes. buffing or chemical brightening.

pickling in hot. Frequent skimming is needed at the points of entry and exit of the wire or strip being galvanized. graphite) · Partial annealing. It involves heating the metal to a specific temperature. usually carried out in a protective atmosphere. improve machinability. is usually an integral part of the processing of metal products. dilute hydrochloric acid..e. Continuous galvanizing of wire requires annealing steps.The continuous galvanizing line for light-gauge strip steel omits pickling and the use of flux. Various types of materials are floated on the surface of the zinc bath to prevent oxidation of the molten zinc. Annealing Annealing is a ―softening‖ heat treatment widely used to allow further cold working of the metal. aimed at obtaining the maximum softness economically feasible · Malleablizing. settles to the bottom of the molten zinc bath and must be removed periodically.g. drying. a special kind of anneal given to iron castings to make them malleable by transforming the combined carbon in the iron to fine carbon (i. it uses alkaline cleaning and maintains the clean surface of the strip by heating it in a chamber or furnace with a reducing atmosphere of hydrogen until it passes below the surface of the molten zinc bath. the heating and cooling of a metal which remains in the solid state. which is carried out in a controlled atmosphere to minimize surface oxidation · Close annealing or box annealing. air or water cooling. a method in which both ferrous and non-ferrous metals are heated in a sealed metal container with or without a packing material and then slowly cooled · Full annealing. A number of annealing techniques are used: · Blue annealing. It almost always involves a change in the crystalline structure of the metal which results in a modification of its properties (e. usually with a molten lead pan in front of the cleaning and galvanizing tanks. application of a flux. in which a layer of blue oxide is produced on the surface of iron-based alloys · Bright annealing.. rinsing. heating and slow cooling to reduce hardness. holding it at that temperature for a specific length of time and allowing it to cool at a particular rate. stress-relieve the product before it is used and so on. heating and quenching to increase hardness. low-temperature heating to minimize internal stresses). an alloy of iron and zinc. Heat treatment Heat treatment. a low-temperature process to remove internal stresses induced in the metal by cold working . annealing to make the metal more malleable. and then galvanizing in the molten zinc bath. A dross.

bearings.g. The metal is heated in an ordinary furnace to above the transformation range and then passes from the furnace directly into. Quench-hardening and tempering An increase in hardness can be produced in an iron-based alloy by heating to above the transformation range and rapidly cooling to room temperature by quenching in oil. in order to increase its toughness.6% carbon steel wire). water or air. it is tempered by reheating to a temperature below the transformation range and allowing it to cool at the desired rate.. a lead bath held at a temperature of about 170°C.g. It is achieved by heating to a temperature about 20°C below the metal’s melting point for about 2 hours or more and then quenching. usually applied to ingots or powdered metal compacts. which produces improved machinability by allowing the iron carbide in the crystalline structure to acquire a spheroid shape. .and case-hardening This is another heat-treatment process applied most frequently to iron-based alloys. gear teeth. It has a number of variations: · Flame hardening involves hardening the surfaces of the object (e. Homogenizing Homogenizing. Patenting Patenting is a special type of annealing process that is usually applied to materials of small crosssection which are intended to be drawn (e. Normalizing A process similar to full annealing. which allows the surface of the object to remain hard while its core remains relatively ductile.. Martempering and austempering are similar processes except that the article is quenched. in a salt or lead bath held at a temperature of 400°C. The article is often too highly stressed to be put into service and. ensures the uniformity of the mechanical properties to be obtained and also produces greater toughness and resistance to mechanical loading. water or another suitable medium. Age-hardening Age-hardening is a heat treatment often used on aluminium-copper alloys in which the natural hardening that takes place in the alloy is accelerated by heating to about 180°C for about 1 hour. slideways) by heating with a high-temperature gas torch and then quenching in oil. Surface.· Sub-critical or spheroidizing annealing. for example. 0. is designed to remove or greatly reduce segregation. for example.

The process is widely known as Schooping. usually ammonia gas. · Cyaniding is a method of case-hardening in which the surface of a low-carbon steel object is enriched in both carbon and nitrogen simultaneously. the gun can also accept the metal in powder form. molybdates and nickel . liquid or gaseous carbonaceous medium (e. zinc. The need to phosphate multi-metal objects and the desire to increase line speeds in automated operations have led to reducing reaction times by the addition of accelerators such as fluorides.g. Schoop who invented it. is a technique for applying a protective metallic coating to a mechanically roughened surface by spraying it with molten droplets of metal. 2 to 5% anhydrous ammonia).g.· Electrical induction hardening is similar to flame hardening except that the heating is produced by eddy currents induced in the surface layers. It usually involves heating the object for 1 hour in a bath of molten 30% sodium cyanide at 870°C. Any metal that can be made into a wire may be used. liquid sodium cyanide and sodium carbonate. It is also used to build up worn or corroded surfaces and for salvaging badly-machined component parts. Phosphating Phosphating is used mainly on mild and galvanized steel and aluminium to augment the adhesion and corrosion resistance of paint. propane or compressed natural gas. manganese. The coiled wire is usually straightened before being fed into the gun. after the Dr. It uses the Schooping gun. It essentially consists of allowing the metal surface to react with a solution of one or more phosphates of iron. or metal spraying. solid charcoal and barium carbonate. · Carburizing increases the carbon content of the surface of an iron-based alloy by heating the object in a solid. and then quenching in oil or water. Vacuum metallizing is a process in which the object is placed in a vacuum jar into which the coating metal is sprayed. methane and so on) at a temperature of about 900°C. · Carbo-nitriding is a gaseous process for the simultaneous absorption of carbon and nitrogen into the surface layer of steel by heating it to 800 to 875°C in an atmosphere of a carburizing gas (see above) and a nitriding gas (e.. Metallizing Metallizing. The heat source is a mixture of oxygen and either acetylene. pistol-shaped spray gun through which the metal in wire form is fed into a fuel gas/oxygen blowpipe flame which melts it and. gaseous carbon monoxide. at about 500 to 600°C.. It is also used to form a layer which acts as a parting film in the deep drawing of sheet metal and improves its wear resistance. chlorates. sodium or ammonium. · Nitriding increases the nitrogen content of the surface of a special low-alloy cast iron or steel object by heating it in a nitrogenous medium. Sodium and ammonium phosphate solutions are used for combined cleaning and phosphating. a hand-held. sprays it onto the object. using compressed air. wax and oil finishes.

In complex primers. alcohols and ethers. . The latter may include plasticizers based on monomeric and polymeric esters and stabilizers such as lead carbonate. The most commonly used plastics include polyethylene. spray. polyamides (nylons) and PVC. fatty acid salts of barium and cadmium. chromium. The primers usually contain resins. ketones. The phosphating sequence typically includes the following steps: · hot caustic cleaning · brushing and rinsing · further hot caustic cleaning · conditioning water rinse · spraying or dipping in hot solutions of acid phosphates · cold water rinse · warm chromic acid rinse · another cold water rinse · drying. or in the form of fabricated sheets which are laminated to the metal surface with an adhesive. The most commonly used resins are polyvinyl butynol. pigments and solvents and may be applied to the prepared metal surfaces by brush. esters. roller coating or electrophoresis. dibutyltin dilaurate. zinc and calcium compounds. Priming Organic paint primers are applied to metal surfaces to promote the adhesion of subsequently applied paints and to retard corrosion at the paint-metal interface. phenolic resins.compounds to the phosphating solutions. The solvents may be any combination of aliphatic and aromatic hydrocarbons. Inorganic pigments used in primer formulations include lead. crystal refining agents such as tertiary zinc phosphate or titanium phosphate are added to the pre-treatment rinse. Plastic coating Plastic coatings are applied to metals in liquid form. isocyanates and urea formaldehyde are used. epoxidized oils.To reduce crystal size and. cross-linking agents such as tetraethylene pentamine. barium. pentaethylene hexamine. increase the flexibility of zinc phosphate coatings. ethyl silicates and chlorinated rubbers. epoxyesters. drying oil alkyds. as powders which are subsequently cured or sintered by heating. consequently. immersion.

adequately drained. For example. slip-resistant floors must be provided. and less hazardous materials should be substituted where possible. Workplace design The workplace should be designed to allow the delivery of raw materials and supplies and the removal of the finished products without interfering with the ongoing processing. mixing of nitrate and cyanide salts by accident could cause an explosion due to the strong oxidizing properties of nitrates.alkyltin mercaptides and zinc phosphate. Many of the metal finishing operations involve liquids. Because of the danger of splashes of hot acid and alkali solutions. Chemical assessment All chemicals should be evaluated for potential toxicity and physical hazards. . Housekeeping must be diligent to keep the work areas and other spaces clean and free from accumulations of materials. Many are regularly encountered in manufacturing operations. Work stations and work assignments should use ergonomic principles to minimize strains. Since many of the chemicals are flammable or prone to react when mixed. By and large. the hazard of fire and explosion must also be considered. excessive fatigue and RSIs. some of the plasticizers are skin sensitizers. since the less toxic material may be more flammable. however. they can be prevented or controlled. Splash guards are essential. Signs should be posted to warn other production and maintenance personnel of such dangers as chemical baths and hot surfaces. However. Systems for disposal of solid and liquid wastes and effluents from furnaces and exhaust ventilation must be designed with environmental concerns in mind. Machine guards must have automatic lockout so the machine is de-energized if the guard is removed. Some systems push fresh air across the tank to ―push‖ airborne contaminants to the exhaust side of the system. Accordingly. and when leaks. In addition. Fresh air intakes must be located away from exhaust vents so that potentially toxic gases are not recirculated. spills or splashes of acids or alkalis occur they must be washed away promptly. Although generally of low toxicity and non-irritating. sprains. proper separation in storage and in transit is essential. Some are potentially life threatening. the chemical compatibility of materials must be considered. others are presented by the uniqueness of the techniques and materials employed. Hazards and Their Prevention As might be deduced from the complexity of the processes outlined above. eyewash fountains and whole-body showers must be installed within easy reach. Ventilation Most of the metal coating processes require LEV that is strategically placed to draw the vapours or other contaminants away from the worker. there is a large variety of safety and health hazards associated with the surface treatment of metals.

goggles with or without face shields as appropriate. the area should be immediately and copiously rinsed with cool. the protective items should be insulated and chemical-resistant. Alkaline and acid solutions The heated alkaline and acid solutions used in cleaning and treatment of metals are particularly corrosive and caustic. Care should be exercised when utilizing chlorinated hydrocarbons as phosgene may result from a reaction of the chlorinated hydrocarbon. aprons or coveralls and shoes).Personal protective equipment Processes should be engineered to prevent potentially toxic exposures. wet items to be cleaned and dried before re-using them. medical attention may be necessary. Insulated gloves and other protective clothing should be available where there is the risk of thermal burns from hot metal. hospitalization are advisable for workers who have been exposed. particularly when the eye is involved.. Skin contact with hydrofluoric acid can cause severe burns without pain for several hours. If there is possible exposure to electricity. because it may take 4 hours or more before the effects on the lungs become apparent. Competence testing and periodic retraining will assure that workers have retained the needed information. Prompt prophylactic medical treatment and. in languages and at educational levels that ensure they will be understood by the workers. MSDSs must be provided for each of the chemical products which explain the chemical and physical hazards. acids and metals. Close supervision is advisable to make sure that the proper procedures are being followed. Eyewash fountains and emergency showers are essential. Employee training and supervision Employee education and training are essential both when new to the job or when there have been changes in the equipment or the process. pneumonitis and even potentially fatal pulmonary oedema may appear belatedly in a worker who apparently had no initial effect from the exposure. so that workers’ clothing remains uncontaminated and workers do not carry toxic materials back into their homes. Bronchitis. Because many of the exposures involve hot corrosive or caustic solutions. . PPE must be available in adequate quantity to allow contaminated.g. employees will have to be provided with appropriate PPE (e. Prompt medical attention is essential. Selected hazards Certain hazards are unique to the metal coating industry and deserve special consideration. often. PPE should be non-conductive. when a splash reaches the skin. Nitric and hydrofluoric acid are particularly dangerous when their gases are inhaled. furnaces and so on. An important adjunct is the availability of wash-up facilities and clean lockers and dressing rooms. gloves. Proper protective clothing and goggles will guard against the inevitable splashes. clean water for at least 15 minutes. but since they cannot always be totally avoided. They are irritating to the skin and mucous membranes and are especially dangerous when splashed into the eye.

ulceration and eczema of the skin and mucosa and a characteristic perforation of the nasal septum. oxygen therapy and inhalation of amyl nitrite. electroplating and cyaniding. but it remains the ubiquitous occupational hazard and must always be guarded against. Hands and clothing must be carefully cleaned following a potential cyanide exposure. Protection is provided by LEV with a safety zone of at least 80 to 100 cm between the source and the breathing area of the worker. mixing and weighing out of these substances in the dry state. crushing and drying of flint. Lead has become less of a problem with the decline of its use in ceramics and porcelain glazes. Optimum cleanliness is essential for workers using cyanide. to become dusts again when they dry out. Certain operations present a risk of silicosis and pneumoconiosis: the calcining. and are most effectively removed by LEV as they are created. LEV and skin protection are essential. the sieving. copious washing of the exposed areas with water. Food should not be eaten before washing. Defatting of the skin by organic solvents may be a precursor of dermatitis. LEV and rigorous cleanliness and personal hygiene are important preventive measures. The lethal concentration in air is 300 to 500 ppm. Ductwork should be designed to be smooth and air velocity should be sufficient to keep the particulates from settling out of the air stream. and the charging of furnaces with such materials. They also represent a danger when they are used in a wet process and are splashed about the workplace and on workers’ clothing. toxicity of the central nervous system and liver and kidney damage are most frequent. First aid measures for cyanide poisoning include transport into the open air. quartz or stone. Fatal exposures may also result from skin absorption or ingestion of cyanides.Dust Metallic and oxidic dusts are a particular problem in grinding and polishing operations. Aluminium and magnesium dust may be explosive and should be collected in a wet trap. Bronchial asthma may occur. In the acute phase. Reaction with acid will form the volatile. their narcotic effects may lead to respiratory paralysis and death. Bench ventilation must also be installed to remove residual vapours from the finished workpieces. removal of contaminated clothing. In chronic exposure. Chromium and nickel Chromic and nickel compounds used in galvanic baths in electroplating may be hazardous. Chromium compounds can cause burns. Cyanide Baths containing cyanides are frequently used in electrolytic degreasing. Beryllium and its compounds have received interest recently due to the possibility of carcinogenicity and chronic beryllium disease. potentially lethal hydrogen cyanide (prussic acid). and should never be in the work area. Organic solvents Solvents and other organic chemicals used in degreasing and in certain processes are dangerous when inhaled. Nickel salts can . Many solvents are also flammable.

a sufficiently large well or pit should be provided to capture the molten metal if this occurs. Lead furnaces may be dangerous since lead tends to vaporize quite rapidly at temperatures above 870°C. The ignition temperature varies from 450 to 750 °C. . under certain circumstances. Fire and explosion Many of the compounds used in metal coating are flammable and. a worker developing a headache on the job should immediately be removed into fresh air. the furnaces and drying ovens are gas fired. The gaseous media (atmospheres) in the furnace may react with the metal charge (oxidizing or reducing atmospheres) or they may be neutral and protective. and their temperature should not exceed 27°C. Furnaces should be properly ventilated and burners protected from being clogged by dripping material. may reach explosive concentrations. See the article ―Welding and thermal cutting‖ in this chapter for detailed precautions. in addition to being combustible. therefore. if not exhausted. Compressed oxygen and fuel gas cylinders used in metallizing are fire and explosion hazards if not stored and operated properly. Quenching oils should have a high flashpoint.cause obstinate allergic or toxic-irritative skin injury. In electrolytic operations. it frequently reaches toxic levels before the worker becomes aware of it. Accordingly. a supply of inert gas (e. hydrogen formed in the process may collect at the surface of the bath and. especially if the metal charge is not completely immersed. Furnaces and ovens Special precautions are needed when working with the furnaces employed. Headache is one of the earliest symptoms of toxicity. and special precautions such as flame-failure devices at burners. Carbon monoxide is perhaps the greatest hazard from furnaces and ovens. LEV and skin protection are essential. Since a cooling furnace tends to suck in air (a particular danger when the fuel or power supply is interrupted). A pot breakage or failure may also be hazardous. for example. and. Oil quenching is also a fire hazard. Danger zones include recessed pockets in which the carbon monoxide may collect. but a local spark may cause ignition even at lower temperatures.g. The danger of explosion is greater when the furnace is being started up or shut down. nitrogen or carbon dioxide) should be available for purging when the furnace is shut down as well as when a protective atmosphere is introduced into a hot furnace. low-pressure cut-off valves in the supply lines and explosion relief panels in the structure of the stoves should be installed. Since it is colourless and odourless. it should be remembered that brickwork is porous and may retain the gas during normal purging and emit it when the purging is completed. explosive.. There is evidence that both chromium and nickel compounds may be carcinogenic. For the most part. Most of the latter contain up to 50% hydrogen and 20% carbon monoxide. form highly explosive mixtures with air at elevated temperatures. which. an effective fume extraction system is required. in the heat treatment of metals where components are handled at high temperatures and the materials used in the process may either be toxic or explosive or both.

fumes. cobalt. most of which can be prevented or controlled by the diligent application of well-recognized preventive measures. acid mists and other potential hazardous materials and risks. However. mercury. cadmium. and modifying plant layout to reduce material handling or re-entrainment of settled dust. Heat The use of furnaces. Workers and supervisors should be trained in the recognition of heat stress symptoms. The engineering controls are basically the same. ovens. heat. selenium. by occlusive protective garments and gear. Some process and/or material handling modifications may be feasible to eliminate or reduce the generation of emissions: minimizing handling. nickel. but supplying cooled air in local ventilation systems is helpful. copper.As required by local ordinances. lead and zinc comprise 95% of the production in the secondary non-ferrous metal industry. Ringenwald. . These reclaimed metals are not distinguishable from the metals produced from primary processing of an ore of the metal. Conclusion Surface treatment of metals involves a multiplicity of processes entailing a broad range of potentially toxic exposures. Metal reclamation is the process by which metals are produced from scrap. (Iron and steel are discussed in the chapter Iron and steel industry. Rest breaks in cool surroundings and adequate fluid intake (fluids taken at the work station should be free of toxic contaminants) will help to avert heat toxicity. Magnesium. precious metals. solvents. Cassady and Richard D.) Control Strategies Emission/exposure control principles Metal reclamation involves exposures to dust. heated solutions and molten metals inevitably presents the risk of excessive heat exposure. lowering pot temperatures. noise. Complete air conditioning of a plant may not be economically feasible. which is compounded in hot. Aluminium. Jr. should be provided and maintained in working order. See also the article ―Copper. decreasing dross formation and surface generation of dust. open flames. particularly. tin and titanium are also reclaimed. METAL RECLAMATION Melvin E. firefighting equipment. and the workers drilled in using it properly. including alarms. the process is slightly different and the exposure could be different. lead and zinc smelting and refining‖ in this chapter. Metal reclamation is very important to the world economy because of the depletion of raw materials and the pollution of the environment created by scrap materials. humid climates and.

supplemented by personal respiratory protection. Because enclosures are seldom air tight. the employees’ time-weighted average exposure to contaminants can be reduced. fewer people are exposed. Reclaim operations are often isolated from other plant operations. where fresh filtered air is supplied to the breathing zone of the employee at the workstation. One of the most common ways to control emissions is to provide local exhaust ventilation at the point of emission generation. If the replacement air system is well designed and integrated into natural and comfort ventilation systems. and the number of emission sources contributing to exposure in any one area will be reduced. This can also reduce ergonomic hazards due to materials handling. towards the emission source and to the exhaust. Thus. replacement air outlets should be placed so clean air flows from the outlet across the employees. more effective control of exposures can be expected. To prevent cross contamination of clean areas in the plant. cleaning and equipment storage should be provided. This technique is often used with supplied-air islands and places the employee between clean incoming air and the emission source. a negative draught exhaust system is often applied to the enclosure.Exposure can be reduced in some cases if machines are selected to perform high-exposure tasks so that employees may be removed from the area. For example. The velocity required to accomplish this will vary from application to application. stand-by pulpits and control rooms. control rooms. Clean areas are intended to be controlled through direct emission controls and housekeeping. it is desirable to isolate processes generating significant emissions. It also prevents secondary employee exposure created by the re-entrainment of settled contaminants. By spending time in a relatively contaminant-free area. The capture velocity of an exhaust hood must be great enough to prevent fumes or dust from escaping the air flow into the hood. . Employees in contaminated areas can be protected by supplied-air service cabs. Capturing emissions at their source reduces the potential for emissions to disperse into the air. Occasionally. maintenance activities. Sufficient space for hoods. The average daily exposure of workers can be reduced by providing clean areas such as breakrooms and lunchrooms that are supplied with fresh filtered air. duct work. This simplifies exposure evaluations and makes the identification and control of major sources easier. The air flow should have enough velocity to carry fume and dust particles into the hood and to overcome the disrupting effects of cross drafts and other random air movements. These areas exhibit low ambient contaminant levels. islands. it is possible to enclose or isolate a specific emission source. A physical barrier will contain emissions and reduce their spread. All exhaust or dilution ventilation systems also require replacement air (known also as ―makeup‖ air systems). Another popular application of this principle is the supplied-air island. The use of recirculation heaters or personal cooling fans which can overcome local exhaust ventilation should be restricted.

they are cost effective but require a responsible and cooperative attitude on the part of employees and line supervisors. These programmes are the responsibility of management and employees. Employees who operate the same equipment on different shifts can have significantly different airborne exposures because of differences in these factors between shifts. safety shoes and work gloves should be routinely worn for all jobs. keeping surfaces free of accumulated dusty materials. Where wheeled-vehicle transport is used. Engineering controls can be defeated by poor work habits. In addition to maintaining general ventilation systems. The attitude of senior management toward safety and health is reflected in the attitude of line supervisors. inadequate maintenance and poor housekeeping or personal hygiene.Wheeled-vehicles are significant sources of secondary emissions. . dilution and make-up air ventilation systems must be properly maintained in order to effectively control air contaminants. Fostering good health and safety attitudes can be accomplished through: · a cooperative atmosphere in which employees participate in the programmes · formal training and educational programmes · emphasizing the plant safety and health programme. encourage and supervise ―good‖ (i. Coatings may be applied to some surfaces to facilitate wash down of roadways. Programmes should be established to teach. All exhaust. Personal protective equipment Safety glasses with side shields. work practice controls are essential to a successful control programme. coveralls. Just as with a ventilation system. Those engaged in casting and melting. represent good managerial practice as well as good common sense. emissions can be reduced by paving all surfaces. or in casting alloys. process equipment must be maintained to eliminate spillage of material and fugitive emissions. Motivating employees and obtaining their trust is necessary in order to have an effective programme.e. low exposure) practices. Likewise. they must be maintained and continually checked to insure that they are functioning properly.. should wear aprons and hand protection made of leather or other suitable materials to protect against the splatter of molten metal. Appropriate paving material such as concrete should be selected after considering factors such as load. if supervisors do not enforce these programmes. use and care of surface. although often neglected. employees attitudes may suffer. Work practice programme implementation Although standards emphasize engineering controls as a means of achieving compliance. Work practice programmes. and by re-directing vehicle exhaust and cooling fan discharge. Work practice programmes cannot be simply ―installed‖. reducing vehicle travel distances and speed.

and the clean. greases.In operations where engineering controls are not adequate to control dust or fume emissions. Borings and turnings are by-product of the machining of castings. Drosses. Clean scrap requiring no pre-treatment is transported to storage or is charged directly into the smelting furnace. zinc. The processes used in this industry include scrap pretreatment. Old scrap. If noise levels are excessive. sweated pig and some primary aluminium. . This process is carried out in a mechanically rotated. and the iron is torn away from the aluminium. Borings and turning are pre-treated in order to remove cutting oils. forging and other solids purchased from the aircraft industry. The metal is tapped periodically through a hole in its base. and cannot be engineered out or noise sources cannot be isolated. · Burning/drying. New scrap consists of clippings. castings and clippings. moisture and free iron. rods and forging by the aircraft and automobile industry. The crushed material is passed over vibrating screens to remove dirt and fines. · Baling. Sorted scrap is conveyed to a crusher or hammer mill where the material is shredded and crushed. hearing protection should be worn. There should also be a hearing conservation programme. Specially designed baling equipment is used to compact bulky aluminium scrap such as scrap sheet. skimmings and slags are obtained from primary reduction plants. especially casting and sheet contaminated with iron. alloying and casting. Old scrap includes automobile parts. Processes Aluminium The secondary aluminium industry utilizes aluminium-bearing scrap to produce metallic aluminium and aluminium alloys. Purchased aluminium scrap undergoes inspection. fabricators and other manufacturing plants. are inputs to this process. household items and airplane parts. remelting. The steps involved are as follows: · Inspection and sorting. · Hot-dross processing. Free iron. refractory-lined barrel. stainless steel. then granulated or further reduced in hammer mills to separate the iron core and plastic coating from the aluminium. appropriate respiratory protection should be worn. secondary smelting plants and foundries. Aluminium can be removed from the hot dross discharged from the refining furnace by batch fluxing with a salt-cryolite mixture. the moisture and organics are volatilized in a gas.or oil-fired rotary dryer. The raw material used by the secondary aluminium industry includes new and old scrap. the remaining material is magnetically treated for iron removal. the dried chips are screened to remove aluminium fines. dried borings are sorted in tote boxes. brass and oversized materials are removed. The scrap is crushed in a hammer mill or ring crusher. including audiometric testing and training. Pure aluminium cable with steel reinforcement or insulation is cut with alligator-type shears. · Shredding/classifying. · Crushing and screening. The aluminium that needs pre-treatment is manually sorted.

carboneous materials associated with aluminium foils are charged and then separated from the metal product. depending on the specifications. Separation of dirt and other non-recoverables from the metal is achieved by screening. Sweating is a pyrometallurgical process which is used to recover aluminium from high-iron-content scrap. Materials are added for processing by batch or continuous feed. Aluminium foil backed with paper. sweated pigs or. such as residues from burned coatings and dirt. collecting pots or holding wells. When demagging with chlorine gas.8 lists exposure and controls for aluminium reclamation operations. High-iron aluminium scrap. Reverberatory furnaces are used to convert clean sorted scrap. Table 82. PPE—respiratory protection when desoldering Local exhaust ventilation and Crushing/screening . · Reverberatory (chlorine) smelting-refining. castings and dross are inputs in this process.8 Engineering/administrative controls for aluminium. Table 82. Demagging is the process which reduces the magnesium content of the molten charge. Open-flame reverberatory furnaces with sloping hearths are generally employed. Alloying agents are then added. untreated scrap into specification alloys. The scrap is charged to the furnace by mechanical means. The higher-melting materials including iron. The product is termed ―sweated pig‖. Engineering/administrative controls Local exhaust ventilation during desoldering. cold aluminium-laden dross and other residues are processed by milling. in some cases. screening and concentrating to obtain a product containing a minimum aluminium content of 60 to 70%. air classification and/or magnetic separation.· Dry milling. · Reverberatory (fluorine) smelting-refining. Ball mills. · Aluminium sweating. gutta-percha or insulation is an input in this process. In the roasting process. This process is similar to the reverberatory (chlorine) smelting-refining process except that aluminium fluoride rather than chlorine is employed. In the dry-milling process. by operation Process equipment Sorting Exposure Torch desoldering—metal fumes such as lead and cadmium Non-specific dusts and aerosol. brass and oxidation products formed during the sweating process are periodically tapped from the furnace. chlorine is injected through carbon tubes or lances and reacts with magnesium and aluminium as it bubbles. to form insolubles which float to the surface as slag. Solvent fluxes are added which react with non-metallics. rod mills or hammer mills can be used to reduce the oxides and non-metallics to fine powders. through a grate and into air-cooled moulds. · Roasting. After the scrap is charged a flux is added to prevent contact with and subsequent oxidation of the melt by air (cover flux). Separation is accomplished as aluminium and other low-melting constituents melt and trickle down the hearth. In the skimming step impure semi-solid fluxes are skimmed off the surface of the melt.

hydrogen flluorides. heat stress work/rest regimen. fluids. and general area ventilation. isolation of noise source. PPE— hearing protection and respiratory protection Local exhaust ventilation. heat stress work/rest regimen. fluids. noise isolation of noise source. carbon monoxide. general area ventilation. fluorine. isolation of noise source. and condensed heavy organics. Gases and vapours containing fluorides. PPE— hearing protection Hot-dross processing Some fumes Dry milling Roasting Dust Dust Local exhaust ventilation. PPE— hearing protection Baling Burning/drying No known exposure Non-specific particulate matter which may include metals. hydrocarbons and aldehydes No controls Local exhaust ventilation. general area ventilation. heat and noise Copper reclamation . metal particulates. metal chlorides. heat stress work/rest regimen. aluminium chlorides. heat stress work/rest regimen. PPE— hearing protection and respiratory protection Sweating Metal fumes and particulates. chlorine. soot. general area ventilation. fluids. isolation of noise source. heat and noise Reverberatory (chlorine) smeltingrefining Products of combustion. heat stress work/rest regimen. general area ventilation Local exhaust ventilation. general area ventilation. fluids. PPE— hearing protection Local exhaust ventilation. metal fluorides. general area ventilation. sulphur dioxide. heat and noise Reverberatory (fluorine) smeltingrefining Products of combustion. general area ventilation Local exhaust ventilation. aluminium fluorides. hydrogen chlorides. chlorides. non-specific gases and vapours. isolation of noise source. PPE— hearing protection and respiratory protection Local exhaust ventilation. fluids. isolation of noise source.oil mists.

The wire scrap is charged in batches to a primary ignition chamber or afterburner. Insulation and lead cable coverings are stripped by hand or by specially designed equipment. automobiles and domestic appliances. drosses.The secondary copper industry utilizes copper-bearing scrap to produce metallic copper and copper based alloys. borings. copper. Old scrap sources include wire. skimmings. clay and metal oxides. thin plate. The primary metal. hammer mills and ball mills. which can be reoxidized to the cupric state by air oxidation. is generally not the melted component. hydrocarbons and aldehydes. electrical equipment. sulphur dioxide. · Shredding. Non-specific particulate matter is generated which may include smoke. sweepings and baghouse dust. foundry ashes. Volatile combustion products are then passed through a secondary combustion chamber or baghouse for collection. · Sweating. drosses. foundry ashes and sweepings from smelters. Ferrous components can be separated magnetically. chlorides. carbon monoxide. Gases and vapours may contain oxides of nitrogen. · Briquetting and crushing. turnings and chips containing volatile organic impurities such as cutting fluids. The raw materials used can be classified as new scrap produced in the fabrication of finished products or old scrap from obsolete worn out or salvaged articles. Borings. Copper can be recovered from relatively clean scrap by leaching and dissolution in a basic ammonium carbonate solution. This process accomplishes the same function as shredding but uses an aqueous separation medium and different input materials such as slags. plumbing fixtures. The equipment used includes hydraulic baling presses. the copper oxide is recovered by steam distillation. . · Drying. turnings and chips are compacted for easier handling. Other materials with copper value include slags. · Insulation burning. The copper oxide is then dried. The shredded material is then sorted by air or hydraulic classification with magnetic separation of any ferrous materials. · Steam distillation. · Grinding and gravity separation. oils and greases are removed. Clean scrap may be manually separated for charging directly to a melting and alloying furnace. The removal of low vapour-melting components from scrap is accomplished by heating the scrap to a controlled temperature which is just above the melting point of the metals to be sweated out. Boiling the leached material from the carbonate leaching process precipitates the copper oxide. After the crude solution is separated from the leach residue. This process separates insulation and other coatings from copper wire by burning these materials in furnaces. Clean wire. Scrap is sorted on the bases of its copper content and cleanliness. The following steps are involved: · Stripping and sorting. The separation of copper wire from insulation is accomplished by reducing the size of the mixture. wire screen. Cupric ions in an ammonia solution will react with metallic copper to produce cuprous ions. · Ammonium carbonate leaching.

the undissolved residue is filtered off. Local exhaust ventilation and oil mists. The air oxidizes copper sulphide and other metals. · Converter smelting. As the anodes dissolve in the electrolyte the impurities settle to the bottom of the cell as a slime. Table 82. · Sulphuric acid leaching. The copper from this process is called blister copper. washed. metal particulates general area ventilation. · Electrolytic refining.9 lists exposures and controls for copper reclamation operations. usually by tipping the furnace and then there is a secondary blow and skim. Molten black copper is charged to converter. The copper is filtered. Ammonium carbonate solution containing copper ions is heated under pressure in hydrogen. dried and sintered under a hydrogen atmosphere. The resulting molten metal is then cast. The blister copper is charged to the refining vessel in an oxidizing atmosphere. The powder is ground and screened. After digestion. by operation Process equipment Stripping and sorting Exposures Air contaminants from material handling and desoldering or scrap cutting Engineering/administrative controls Local exhaust ventilation. which is a pear-shaped or cylindrical steel shell lined refractory brick. The copper from the anode is ionized and the copper ions are deposited on a pure copper starter sheet. Scrap copper is dissolved in hot sulphuric acid to form a copper sulphate solution for feed to the electrowinning process. Table 82. general area ventilation Briquetting and crushing Non-specific dusts and aerosol. precipitating the copper as a powder. This slag is skimmed from the furnace. wire Local exhaust ventilation and Shredding . The blister copper from the converter is fire refined in a cylindrical tilting furnace.9 Engineering/administrative controls for copper. the refined copper will be cast as an anode.· Hydrothermal hydrogen reduction. If the copper is to be electrolytically refined. PPE—hearing protection and respiratory protection Non-specific dusts. The blister copper is generally further refined in a fire refining furnace. A flux containing silica is added to react with the iron oxides to form an iron silicate slag. The cathode copper produced is melted and cast into a variety of shapes. Air is blown into the molten charges through nozzles called tuyères. This slime can be additionally processed to recover other metal values. and noise isolation of noise source. a vessel like a reverberatory furnace. The anodes from the fire refining process are placed in a tank containing sulphuric acid and a direct current. · Fire refining. The impurities are skimmed from the surface and a reducing atmosphere is created by the addition of green logs or natural gas.

general area ventilation. PPE—hearing protection and respiratory protection Local exhaust ventilation. isolation of noise source. general area ventilation. metal particulates and noise general area ventilation. PPE—hearing protection and respiratory protection Local exhaust ventilation. isolation of noise source. work/rest regimen. slags and drosses. PPE—respiratory protection Sweating Local exhaust ventilation. chlorides. which may include metals. PPE—glasses with side shields Local exhaust ventilation. carbon monoxide. work/rest regimen. general area ventilation. general area ventilation Ammonium carbonate leaching Steam distillation Ammonia Ammonia Hydrothermal hydrogen Ammonia reduction Sulphuric acid leaching Sulphuric acid mists . isolation of noise source. hydrocarbons and aldehydes Metal fumes and particulates. isolation of noise source. carbon monoxide. PPE—hearing protection and respiratory protection Local exhaust ventilation and general area ventilation. general area ventilation. fluids. vapours and particulates Insulation burning Local exhaust ventilation. soot and condensed heavy organics Gases and vapours containing fluorides. work/rest regimen. isolation of noise source. metal particulates from fluxes. chlorides. PPE—respiratory protection Local exhaust ventilation. clay and metal oxides Gases and vapours containing oxides of nitrogen.insulation material. PPE—hearing protection and respiratory protection Grinding and gravity separation Non-specific dusts. hydrocarbons and aldehydes Non-specific particulate matter which may include smoke. PPE—respiratory protection Local exhaust ventilation. non-specific gases. and noise Drying Non-specific particulate matter. fluids. fluids. sulphur dioxide. sulphur dioxide. general area ventilation. general area ventilation.

clothing. The four most common processes for breaking automotive batteries are: 1. Automotive batteries The most common raw material at a secondary lead smelter is junk automotive batteries. sulphur and nitrogen oxides. carbon monoxide. particulates general area ventilation. noise Sulphur oxides. slow speed saw 3. Approximately 50% of the weight of a junk automotive battery will be reclaimed as metallic lead in the smelting and refining process. Most of these processes can generate metal fumes. skin and hair. PPE—hearing protection Sulphuric acid and metals from Local exhaust ventilation. Approximately 90% of the automotive batteries manufactured today utilize a polypropylene box or case. In automotive battery breaking there is a potential for forming arsine or stibine due to the presence of arsenic or antimony used as hardening agents in grid metal and the potential for having nascent hydrogen present.Converter smelting Volatile metals. hydrocarbons. shear . in particular lead and antimony. The polypropylene cases are reclaimed by almost all secondary lead smelters due to the high economic value of this material. sludge general area ventilation Electrolytic refining Lead reclamation Raw materials purchased by secondary lead smelters may require processing prior to being charged into a smelting furnace. It should be noted that lead dust can generally be found throughout lead reclamation facilities and that any vehicular air is likely to stir up lead dust which can then be inhaled or adhere to shoes. PPE—respiratory protection and hearing protection Local exhaust ventilation. PPE—hearing protection Electric crucible smelting Fire refining Particulate. This section discusses the most common raw materials which are purchased by secondary lead smelters and feasible engineering controls and work practices to limit employee exposure to lead from raw materials processing operations. Local exhaust ventilation. high speed saw 2. general area ventilation. soot. noise Local exhaust ventilation. general area ventilation.

both lead bearing and cases. Removing the case may generate acid mists. These types of materials may be charged directly into smelting furnaces or mixed with other charge materials. whole battery crushing (Saturn crusher or shredder or hammer mill). or lead-bearing material. an employee manually dumps the groups or lead-bearing material into a pile and places the case and top of the battery into another pile or conveyance system. scrap metallic lead such as linotype and cable covering. Automotive battery separation takes place after automotive batteries have been broken in order that the lead-bearing material can be separated from the case material. Industrial batteries which were used to power mobile electric equipment or for other industrial uses are purchased periodically for raw material by most secondary smelters.4. Groups fall through the slots in the tumbler while the cases are conveyed to the far end and are collected as they exit. Battery pieces. This is used by the vast majority of secondary lead smelters and remains the most widely used technique in small to mid-sized smelters. are placed in a series of tanks filled with water. drosses from lead refining. Materials are transported by fork-lifts. These materials include battery manufacturing plant scrap. front-end loaders or mechanical conveyors (screw. · A sink/float process. Other purchased lead-bearing scrap Secondary lead smelters purchase a variety of other scrap materials as raw materials for the smelting process. The most widely used techniques for accomplishing this task are: · The manual technique. then dumping the groups. The sink/float process typically is combined with the hammer mill or crushing process for battery breaking. . Lead bearing material sinks to the bottom of the tanks and is removed by screw conveyor or drag chain while the case material floats and is skimmed off the tank surface. and tetraethyl lead residues. Many of these batteries have steel cases which require removal by cutting the case open with a cutting torch or a hand-held gas powered saw. The fourth process involves crushing the entire battery in a hammer mill and separating the components by gravity separation. Plastic and rubber battery cases and tops are further processed after being separated from the lead bearing material. transportation and storage of raw material. The first three of these processes involve cutting the top off of the battery. · A tumbler device. bucket elevator or belt). Ribs inside the tumbler dump the groups as it slowly rotates. The primary method of material transporting in the secondary lead industry is mobile equipment. Raw material handling and transport An essential part of the secondary lead smelting process is the handling. After the battery passes through the saw or shear. Batteries are placed into a tumbler device after the tops have been sawed/sheared off to separate the groups from the cases.

Reverberatory furnace tapping operations are very similar to blast-furnace tapping operations. Some environmental hazards associated with blast furnace operations are metal fumes and particulates (especially lead and antimony). Reverberatory furnaces in the secondary lead industry typically have a sprung arch or hanging arch constructed of refractory brick. . Common products are soft (pure) lead and various alloys of hard (antimony) lead. Refining Lead refining in secondary lead smelters is conducted in indirect fired kettles or pots. Blast air for the combustion process enters the blast furnace through tuyères which occasionally begin to fill with accretions and must be physically punched. Many of the contaminants and physical hazards associated with reverberatory furnaces are similar to those of blast furnaces. noise and carbon monoxide. Metal from the smelting furnaces is typically melted in the kettle. belt conveyors and bucket elevators. Such mechanisms can be a hydraulic ram. A variety of charge material conveying mechanisms are used in the secondary lead industry. Some smelters tap metal directly into a holding kettle which keeps the metal molten for refining. then the content of trace elements is adjusted to produce the desired alloy. After the accretions have been punched. to keep them from being obstructed. Reverberatory furnaces are charged with lead-bearing raw material by a furnace charging mechanism. Other devices in use include vibratory hoppers. coke (fuel) limestone and iron (flux).Some common mechanical conveyance methods which are used by secondary lead smelters include: belt conveying systems that can be used to transport furnace feed material from storage areas to the furnace charring area. screw conveyors for transporting flue dust from the baghouse to an agglomeration furnace or a storage area or bucket elevators and drag chains/lines. a screw conveyor or other devices similar to those described for blast furnaces. usually with a steel rod. Blast furnace tapping operations involve removing the molten lead and slag from the furnace into moulds or ladles. heat. The skip hoist is probably the most common. The remaining smelters cast the furnace metal into blocks and allow the blocks to solidify. The conventional method to accomplish this task is to remove the cover of the tuyères and insert the steel rod. These materials are fed into the furnace at the top of the furnace shaft or through a charge door in the side of the shaft neat the top of the furnace. the cover is replaced. Blast furnaces are charged with lead-bearing material. Smelting The smelting operation at a secondary lead smelter involves the reduction of lead-bearing scrap into metallic lead in a blast furnace or reverberatory.

work/rest regimen.Virtually all secondary lead refining operations employ manual methods for adding alloying materials to the kettles and employ manual drossing methods. by operation Process equipment Vehicles Exposures Lead dust from roads and splashing water containing lead Engineering/administrative controls Water washdown and keeping areas wetted down. Table 82. Operator training. It is also preferable to equip belt conveyor systems with selfcleaning tail pulleys or belt wipes if they are used to transport furnace feed materials or flue dusts. Reverberatory furnace Refining Lead particulates and possibly . heat and noise. general area ventilation. acid mists Lead dust Metal fumes and particulates Local exhaust ventilation. heat and noise Local exhaust ventilation. fluids. antimony). general area ventilation. general area ventilation Local exhaust ventilation. Enclose equipment and provide a positive pressure filtered air system. isolation of noise source. general area ventilation Conveyors Lead dust Battery decasing Charge preparation Blast furnace Lead dust. prudent work practices and good housekeeping are key elements in minimizing lead emissions when operating mobile equipment. Dross is swept to the rim of the kettle and removed by shovel or large spoon into a container.10 lists exposures and controls for lead reclamation operations. antimony). carbon monoxide work/rest regimen. (lead. Local exhaust ventilation. isolation of noise source. PPE— respiratory protection and hearing protection Metal fumes and particulates (lead. PPE— respiratory protection and hearing protection Local exhaust ventilation.10 Engineering/administrative controls for lead. fluids. Table 82.

The processes are as follows: · Reverberatory sweating. aluminium. Included in the old scrap category are old zinc engravers’ plates. cadmium. The reduced material is then separated in a screening or pneumatic classification step. or to collecting vessels. sulphur oxides. and zinc metal is collected in kettles situated outside the furnace. The scrap is charged to the furnace.alloying metals and fluxing agents. In this process zinc scrap. The scrap is first crushed and washed. · Sodium carbonate leaching. such as automobile grilles and licence plate frames. The aqueous portion is treated with sodium carbonate.and copper-based alloys from galvanizing and die-casting pots. . · Rotary sweating. In this step. Scrap die-cast products. noise Casting Lead particulates and possibly alloying metals general area ventilation. Various zinc salt contaminants can be produced. die castings. · Muffle sweating and kettle (pot) sweating. die-vapour-cast products. PPE— hearing protection Local exhaust ventilation. and rod and die scrap. manganese and chromium. The metal from this process is sent to distillation or alloying process. · Crushing/screening. In these processes zinc scrap. flue dust and chemical residue as sources of zinc. die-cast skimmings. The zinc oxide is then reduced to zinc metal. iron. Unmeltable material. Contaminants are similar to those of reverberatory sweating. The melt is skimmed. Zinc residues are pulverized or crushed to break down physical bonds between metallic zinc and contaminant fluxes. Crushing can produce zinc oxide and minor amounts of heavy metals and chlorides. refining or alloying. Contaminants are similar to those of reverberatory sweating. general area ventilation Zinc reclamation The secondary zinc industry utilizes new clippings. galvanizers’ dross. copper. such as melting. die-cast products. the zinc is leached out of the material. Most of the new scrap processed is zinc. the material sweated and the sweated zinc is sent to refining or alloying processes. residues and skimmings are charged to a direct-fired furnace and melted. residues and skimmings are charged to the muffle furnace. The high-melting residue is removed and the molten zinc flows out of the furnace directly to subsequent processes. and zinc skins or residues are starting materials for the process. Other contaminants are fluxing agents. Sweating furnaces are used to separate zinc from other metals by controlling the furnace temperature. chlorides and fluorides. The precipitate is dried and calcined to yield crude zinc oxide. causing zinc to precipitate. Metal contaminants include zinc. The residue is removed by a shaker screen which separates the dross from the slag. Residues are chemically treated to leach out and convert zinc to zinc oxide. skimmings and ashes. the slag. lead. flux is added and the contents melted. is then removed prior to recharging.

· Alloying. in this process. · Retort distillation/oxidation and muffle distillation/oxidation. sulphur oxides. as well as other metal particulate and oxides of sulphur exposure. Zinc oxide fumes. Table 82. Excess air is present to insure complete oxidation and to cool the product. iron. lead. manganese and work/rest regimen. the condenser is bypassed and combustion air is added. · Muffle distillation. chlorides and fluorides Rotary sweating Particulates containing zinc. iron.11 lists exposures and controls for zinc reclamation operations. chlorides. copper. by operation Process equipment Exposures Engineering/administrative controls Local exhaust ventilation. The muffle distillation process is used to reclaim zinc from alloys and to manufacture pure zinc ingots. general area ventilation. aluminium. are potential exposures. The vapour is discharged through an orifice into an air stream. The bath is agitated to form a dross that can be skimmed from the surface. crucible. manganese and chromium. general area ventilation. The residue is removed periodically from the muffle. non-specific gases and vapours. The process is similar to retort distillation through the vaporization step. Each of these distillation processes can lead to zinc oxide fume exposures. electric induction melting. Particulates containing zinc. fluids chromium. ammonia and ammonium chloride. Spontaneous combustion occurs inside a refractory vapour-lined chamber. alloying metals. but. The product of the retort distillation/oxidation and muffle distillation/oxidation processes is zinc oxide. copper. reverberatory. as well as heat. fluids Reverberatory sweating Particulates containing zinc. The product is carried by the combustion gases and excess air into a baghouse where the product is collected. The process is semi-continuous which involves charging molten zinc from a melting pot or sweating furnace to the muffle section and vaporizing the zinc and condensing the vaporized zinc and tapping from the condenser to moulds. . hydrogen chloride and zinc chloride can be produced. cadmium. the dross skimmed. aluminium. Table 82. and the metal is cast into various shapes. The contents are then mixed. The function of this process is to produce zinc alloys from pre-treated scrap zinc metal by adding to it in a refining kettle fluxes and alloying agents either in the solidified or molten form. contaminants from fluxing agents. contaminants from fluxing agents. Local exhaust ventilation.· Kettle (pot). cadmium.11 Engineering/administrative controls for zinc. sulphur oxides. heat stress–work/rest regimen. lead. The scrap is charged to the furnace and fluxes are added. After the furnace has been skimmed the zinc metal is poured into ladles or moulds.

The greatest danger in handling magnesium is that of fire. fluids chromium. non-specific gases and vapours. Small fragments of the metal can readily be ignited by a spark or flame. cadmium. contaminants from fluxing agents. New scrap consists of clippings. sodium carbonate. fluids Local exhaust ventilation. skimmings. aluminium. Scrap is added to a crucible. lead. fluids Local exhaust ventilation. . oxides of sulphur and muffle distillation Graphite rod resistor distillation Zinc oxide fumes. work/rest regimen. zinc hydroxide. Local exhaust ventilation.chlorides and fluorides Muffle sweating and kettle (pot) sweating Particulates containing zinc. other metal particulates. The molten magnesium is then cast into ingots. sorted on the basis of weight. general area ventilation. fluids Kettle (pot) melting crucible. This process is used to separate magnesium and magnesium-alloy fractions from other metals present in the scrap. sulphur oxides. chlorides Local exhaust ventilation. zinc carbonate. general area ventilation. ammonia. retort Zinc oxide fumes. minor amounts of heavy metals. alloying metals. chlorides. Local exhaust ventilation. oxides of sulphur Magnesium reclamation Old scrap is obtained from sources such as scrap automobile and aircraft parts and old and obsolete lithographic plates. general area ventilation hydrogen chloride. copper. general area ventilation. chlorides and fluorides Zinc oxide. heated and a flux consisting of a mixture of calcium. · Open pot melting. other metal distillation/oxidation particulates. general area ventilation. turnings. drosses and defective articles from sheet mills and fabrication plants. zinc chloride Zinc oxide fumes. iron. work/rest regimen. work/rest regimen. slags. · Hand sorting. manganese and work/rest regimen. The scrap is spread out manually. general area ventilation Crushing/screening Sodium carbonate leaching Zinc oxide. hydrogen chloride. electric induction melting Alloying Retort distillation. as well as some sludges from primary magnesium smelters. work/rest regimen. reverberatory. borings. ammonia chloride. sodium and potassium chlorides is added. general area ventilation. fluids Local exhaust ventilation. heat Local exhaust ventilation. zinc chloride Particulates containing zinc. This process is used to separate magnesium from contaminants in the sorted scrap.

Mercury vapour can contaminate each of these processes. The filtered mercury is fed to the oxygenation process and the solids which do not pass through the filters are sent to retort distillation. general area ventilation. mercury from dismantled chlor-alkali plants and mercury-containing instruments. · Vacuum distillation.12 lists exposures and controls for magnesium reclamation operations. · Crushing. heat and a high potential for fires Engineering/administrative controls Water washdown Local exhaust ventilation and general area ventilation and work practices Local exhaust ventilation. fluids Casting Mercury reclamation The major sources for mercury are dental amalgams. The steps involved are: leaching the raw liquid mercury with dilute nitric acid to separate metallic impurities. organic chemicals and acid mists. decanting to separate the mercury from the acid. the contaminated liquid mercury is sent to the filtering process. . scrap mercury batteries. sludges from electrolytic processes that use mercury as a catalyst.12 Engineering/administrative controls for magnesium. In addition to mercury vapour there can be exposure to solvents. work/rest regimen. Insoluble impurities such as dirt are removed by passing the mercury-vapour bearing scrap through a filter media. washing with water to remove the residual acid. · Solution purification. After the containers are crushed. agitating the acid-mercury with compressed air to provide good mixing. plastic and glass containers. Purified mercury is collected and sent to the bottling operation. · Filtration. The residue remaining in the heating pot is sent to the retorting process to recover the trace amounts of mercury that were not recovered in the vacuum distillation process. Table 82. by operation Process equipment Scrap sorting Open pot melting Exposures Dust Fumes and dust. Mercury charge is vaporized in a heating pot and the vapours are condensed using a water-cooled condenser. Vacuum distillation is employed to refine contaminated mercury when the vapour pressures of the impurities are substantially lower than that of mercury. and filtering the mercury in a medium such as activated carbon or silica gel to remove the last traces of moisture. a high potential for fires Dust and fumes. The crushing process is used to release residual mercury from metal. This process removes metallic and organic contaminants by washing the raw liquid mercury with a dilute acid.Table 82.

PPE— respiratory protection Local exhaust ventilation. condensing the mercury vapour in water-cooled condensers. PPE—respiratory protection Local exhaust ventilation. collecting the condensed mercury in a collecting vessel. The oxidation process involves two steps. · Retorting. solvents. which can be found as old or new scrap. Sorting produces dust exposures. The following steps are involved in nickel reclamation: · Sorting. Old scrap comprises alloys that are salvaged from machinery and airplane parts. PPE— respiratory protection Local exhaust ventilation.13 lists exposures and controls for mercury reclamation operations. PPE—respiratory protection Local exhaust ventilation.· Oxygenation. general area ventilation. The retorting process is used to produce pure mercury by volatilizing the mercury found in solid mercury-bearing scrap. by operation Process equipment Crushing Filtration Exposures Volatile mercury Volatile mercury Engineering/administrative controls Local exhaust. Table 82. In the sparging step.13 Engineering/administrative controls for mercury. After sparging. The scrap is inspected and manually separated from the non-metallic and non-nickel materials. turnings and solids which are by-products of the manufacture of alloy products. PPE— respiratory protection Vacuum distillation Volatile mercury Solution purification Oxidation Retorting Volatile mercury. sparging and filtering. .and aluminium-vapour based alloys. The steps involved in retorting are: heating the scrap with an external heat source in a closed still pot or stack of trays to vaporize the mercury. This process refines the filtered mercury by removing metallic impurities by oxidation with sparging air. organics and acid mists Volatile mercury Volatile mercury Nickel reclamation The principal raw materials for nickel reclamation are nickel-. copper. the mercury is filtered in a charcoal bed to remove the solid metal oxides. contaminated mercury is agitated with air in a closed vessel to oxidize the metallic contaminants. while new scrap refers to sheet scrap. Table 82. PPE— respiratory protection Local exhaust ventilation.

work/rest regimen. Table 82. heat. by operation Process equipment Sorting Degreasing Exposures Dust Solvent Engineering/administrative controls Local exhaust and solvent substitution Local exhaust ventilation and solvent substitution and/or recovery. This process involves casting the molten metal from the smelting furnace or the refining reactor into ingots. Heat and metal fume exposures are possible. · Ingot casting. Old scrap includes electronic components from obsolete military and civilian equipment and scrap from the dental industry. dust. general area ventilation Local exhaust ventilation. heat Refining Fumes. There can be solvent exposure during degreasing. noise Casting Heat. dust.· Degreasing. noise and heat exposures are possible. fluids Smelting Fumes. followed by lime and silica. Scrap is charged to an electric arc furnace and a reducing agent added. fluids.14 Engineering/administrative controls for nickel. work/rest regimen. Fumes. The molten metal is introduced into a reactor where cold-base scrap and pig nickel are added. fluids. noise and heat exposures are possible. New scrap is generated during the fabrication and manufacturing of precious .14 . The charge is melted and is either cast into ingots or sent directly to a reactor for additional refining. The mixture is filtrated or centrifuged to separate the nickel scrap. metal fumes Precious metals reclamation The raw materials for the precious metal industry consist of both old and new scrap. work/rest regimen. Alloying materials such as manganese. noise. · Reactor refining. Fumes. Nickel scrap is degreased by using trichloroethylene. columbium or titanium are then added to produce the desired alloy composition. Exposures and control measures for nickel reclamation operations are listed in table 82. The spent solvent solution of trichloroethylene and grease goes through a solvent recovery system. general area ventilation. The metal is poured into moulds and allowed to cool. general area ventilation. The ingots are removed from the moulds. dust. · Smelting (electric arc or rotary reverberatory) furnace. PPE—respiratory protection and hearing protection Local exhaust ventilation. PPE—respiratory protection and hearing protection Local exhaust ventilation. usually lime. dust.

metal products. This process is designed to further purify the black copper by blowing air through the melt in a converter. respectively. in table 82. Acid mist exposures are possible. which is then treated with nitric acid and leaves a residue from which the platinumgroup metals can be selectively precipitated. combustion gases and dust Dust. Slag-containing metal contaminants are removed and recycled to the blast furnace. PPE— hearing protection and respiratory .15 (see also ―Gold smelting and refining‖). The copper bullion containing the precious metals is cast into moulds. · Converter smelting. producing black copper which contains the precious metals. · Incineration process. Treated scrap is charged to a blast furnace. by operation. The hard slag that is formed contains most of the slag impurities. PPE—hearing noise hazard protection Organics. Precious metal-bearing scrap is hand sorted and crushed and shredded in a hammer mill. Cyanide-based processes are used to recover gold and silver. Table 82. The electrolyte used is copper sulphate.15 Engineering/administrative controls for precious metals. The precious metal precipitates are then either melted or ignited in order to collect the gold and silver as grains and the platinum metals as sponge. The platinum-group metals can be recovered by dissolving them in molten lead. The products are the elemental metals such as gold. Exposures and controls are listed. Organic chemicals. Sorted scrap is incinerated to remove paper. The precious metal slime from the electrolytic refining process is chemically treated to recover the individual metals. There can be acid exposures. noise Local exhaust ventilation and general area ventilation Local exhaust ventilation. followed by precipitation with ferrous sulphate or sodium chloride to recover the gold and silver. Copper bullion serves as the anode of an electrolytic cell. Hammer mills are noisy. along with coke. Pure copper thus plates out on the cathode while the precious metals fall to the bottom of the cell and are collected as slimes. flux and recycled slag metal oxides. combustion gases and dust exposures are possible. plastic and organic liquid contaminants. · Chemical refining. · Blast-furnace smelting. which can also be recovered by dissolving them in aqua regia solution and/or nitric acid. · Electrolytic refining. Dust and noise may be present. silver. Precious metal processing includes the following steps: · Hand sorting and shredding. The charge is melted and slagged. by operation Process equipment Sorting and shredding Incineration Blast furnace smelting Exposures Engineering/administrative controls Hammermill is a potential Noise control material. platinum and palladium.

Casting can produce cadmium dust and fumes and heat. by operation . hardware and fasteners. New scrap is normally cadmium vapour bearing rejects and contaminated by-products from industries which handle the metals. household appliances. cadmium contacts from switches and relays and other used cadmium alloys. · Melting/dezincing. The solvent and stripped grease are then condensed and separated with the solvent being recycled. If zinc is present in the metal. · Smelting/refining. The reclamation processes are: · Pre-treatment. Products of oil and gas combustion exposures and zinc and cadmium dust may be present. Cadmium dust exposures are possible. Degreased scrap alloy is charged to a retort and heated to produce cadmium vapours which are subsequently collected in a condenser.16 Engineering/administrative controls for cadmium.protection Electrolytic refining Chemical refining Acid mists Acid Local exhaust ventilation. The molten metal is then ready for casting. The scrap pre-treatment step involves the vapour degreasing of alloy scrap. Cadmium metal is charged to a melting pot and heated to the molten stage. general area ventilation Local exhaust ventilation. Among potential exposures are cadmium fumes and dust. cadmium batteries. Exposures in cadmium reclamation processes and the necessary controls are summarized in table 82. · Casting. zinc fumes and dust. · Retort distillation. Table 82. hydrogen chloride and heat.16 . fluxes and chlorinating agents are added to remove the zinc. general area ventilation. zinc chloride. PPE—acid-resistant clothing. chemical goggles and face shield Cadmium reclamation Old cadmium-bearing scrap includes cadmium-plated parts from junked vehicles and boats. Solvent vapours generated by heating recycled solvents are circulated through a vessel containing scrap alloys. chlorine. pre-treated alloy scrap or elemental cadmium scrap is processed to remove any impurities and produce cadmium alloy or elemental cadmium. The casting operation forms the desired product line from the purified cadmium alloy or cadmium metal produced in the previous step. In the smelting/refining operation. There can be exposure to cadmium dust and solvents.

Distillation and retort smelting can produce combustion gases and dust.Process equipment Scrap degreasing Alloy smelting/refining Retort distillation Melting/dezincing Exposures Solvents and cadmium dust Products of oil and gas combustion. PPE—respiratory protection chloride. Local exhaust ventilation. general zinc fumes and dust. fluids. zinc area ventilation. work/rest regimen.17). This process purifies and concentrates pre-treated scrap in a retort distillation operation by melting the scrap and separating selenium from the impurities by distillation. heat stress Cadmium dust and fumes. by operation Process equipment Scrap pretreatment Exposures Dust Engineering/administrative controls Local exhaust . general area ventilation. Selenium dusts may be present throughout. distilled and the selenium vapours are condensed and transferred as molten selenium to a product formation operation.The reclamation processes are as follows: · Scrap pre-treatment. · Distillation. PPE— respiratory protection Local exhaust ventilation. Retort smelting is noisy. chlorine. Insoluble impurities are removed by filtration and the filtrate is treated to precipitate selenium. cadmium dust and fumes Cadmium fumes Engineering/administrative controls Local exhaust and solvent substitution Local exhaust ventilation and general area ventilation. Table 82. · Refining. The selenium is melted. heat Local exhaust ventilation.17 Engineering/administrative controls for selenium. Sulphur dioxide mist and acid mist are present in refining. work/rest regimen. chloride. zinc fumes. PPE—respiratory protection Casting Selenium reclamation Raw materials for this segment are used xerographic copying cylinders and scrap generated during the manufacture of selenium rectifiers. hydrogen fluids. This process separates selenium by mechanical processes such as the hammer mill or shot blasting. Metal dusts can be produced from casting operations (see table 82. This process produces a high vapour purity selenium. This process achieves a purification of scrap selenium based on leaching with a suitable solvent such as aqueous sodium sulphite. · Retort smelting. PPE— respiratory protection Cadmium fumes and dust.

Dusts can be present. except that selenium vapour. · Pickling and chemical treatment process. The solvent-oil-grease vapour mixture is then condensed and the solvent is recovered. Solvent exposures are possible.Retort smelting Combustion gases and dust. Acid mists are a possible exposure. · Casting. The processes of reclamation are: · Hand sorting. general area ventilation Refining Distillation Quenching Casting · Quenching. oxides and rust. · Vacuum melting. general area ventilation Local exhaust ventilation. Degreased scrap is blasted with grit to remove dirt. These shapes are produced by pouring molten selenium into moulds of the proper size and shape and cooling and solidifying the melt. general area ventilation Local exhaust ventilation. · Degreasing. Sorted dirty scrap is charged to a degreasing unit where vapours of perchloroethylene are circulated. This is a dusty operation. The shot is then dried. This process is used to produce selenium ingots or other shapes from the molten selenium. acid mist Dust and combustion products Metal dust Selenium fumes Local exhaust ventilation and general area ventilation. The steps required to produce powder are the same. This process is used to produce purified selenium shot and powder. nickel-base and non-processable components. · Blasting. and obsolete or worn engine parts and turbine blades. rather than molten selenium. The selenium melt is used in producing a shot. is the material which is quenched. Cobalt reclamation The sources of cobalt scrap are super alloy grindings and turnings. . Raw scrap is hand sorted to identify and separate the cobalt-base. noise SO2. depending on the grit used. There can be exposure to heavy metals. Scrap from the blasting operation is treated with acids to remove residual rust and oxide contaminants. control of burner noise Local exhaust ventilation. PPE—hearing protection. This solvent removes the grease and oil on the scrap. PPE— chemical goggles Local exhaust ventilation. Cleaned scrap is charged to a vacuum furnace and melted by electric arc or induction furnace.

A hot solution of sodium hydroxide and sodium nitrite or nitrate is added to dealuminized or raw scrap. Tin dust and acid mists can be found in many of the processes. general area ventilation Local exhaust ventilation. Draining and pumping the . pumping the sodium aluminate to a refining operation to recover soluble tin and recovering the dealuminized tin scrap for feed. Table 82. separating the sodium aluminate solution from the scrap residue. PPE— respiratory protection Local exhaust ventilation. fluids Pickling and chemical treatment process Vacuum melting Casting Heavy metals Heat Tin reclamation The major sources of raw materials are tin-plated steel trimmings. This process extracts the tin in scrap. local exhaust and solvent substitution Dust—toxicity dependent upon Local exhaust ventilation. work/rest regimen. general area ventilation. PPE the grit used for physical hazard and respiratory protection depending on grit used Acid mists Local exhaust ventilation.· casting. Molten alloy is cast into ingots. rejected plating coils from the steel industry. by operation Process equipment Hand sorting Degreasing Blasting Exposures Dust Solvents Engineering/administrative controls Water washdown Solvent recovery. tin drosses and sludges. Heat stress is possible. · Chemical detinning. rejects from tin-can manufacturing companies. In this process hot sodium hydroxide is used to leach aluminium from tin-can scrap by contacting the scrap with hot sodium hydroxide. solder drosses and sludges. · Batch mixing.18 for a summary of exposures and controls for cobalt reclamation. · Dealuminization. used bronze and bronze rejects and metal type scrap.18 Engineering/administrative controls for cobalt. See table 82. general area ventilation. This process is a mechanical operation which prepares a feed suitable for charging to the smelting furnace by mixing drosses and sludges with a significant tin content.

· Evapocentrifugation. fluxing with sulphur to remove copper as matte. drying the leached dust in a dryer and conveying the tin and lead rich dust back to the batch mixing process. · Smelting. pouring the molten tin and casting the molten tin. cobalt and nickel are precipitated as sulphides. · Electrolytic refining. melting the tin metal formed.solution to a refining/casting process are performed when the detinning reaction is complete. The sodium stannate is concentrated from the purified solution by evaporation. · Fire refining. This process converts the hydrated tin oxides to anhydrous stannic oxide by calcining the hydrate and removing and packaging the stannic oxides. cadmium. Impurities such as silver. removing the impurities as slag and dross. some iron. · Settling and leaf filtration. pouring the molten metal and casting the metallic tin. by operation . removing the cathodes after the tin has been deposited and stripping the tin from the cathodes. fluxing with aluminium to remove antimony and casting molten metal into desired shapes. This process is used to purify crude furnace metal by charging a preheated kettle with it. See table 82. This process produces purified tin from the cathodic tin by melting the charge. This process produces cathodic-pure tin from the purified sodium stannate solution by passing the sodium stannate solution through electrolytic cells. filtering the resulting mixture to separate the acid and dissolved zinc and chlorine from the leached dust. copper. skimming the dross. tapping the crude furnace metal and tapping the mattes and slags. · Acidification and filtration. This hydrated oxide can either be processed to produce the anhydrous oxide or smelted to produce elemental tin. drying the dross to remove the impurities as slag and matte. This process purifies the sodium stannate solution produced in the chemical detinning process. · Dross smelting. · Kettle refining. This process produces a hydrated tin oxide from the purified sodium stannate solution. mercury. crystallization of sodium stannate and recovery of sodium stannate is by centrifugation. This process removes the zinc and chlorine values from flue dust by leaching with sulphuric acid to remove zinc and chlorine. The detinned scrap is then washed. Table 82.19 for a summary of exposures and controls for tin reclamation. This process is used to produce tin when electrolytic refining is not feasible. The hydrated oxide is neutralized with sulphuric acid to form the hydrated tin oxide and filtered to separate the hydrate as filter cake. This is accomplished by reducing the hydrated tin oxide with a reducing agent. This process is used to partially purify drosses and produce crude furnace metal by melting the charge. · Dust leaching and filtration. · Calcining.19 Engineering/administrative controls for tin.

fumes. PPE—chemical goggles and/or face shield Local exhaust ventilation. Home scrap which is generated by the milling and manufacturing of titanium products includes trim sheets. fluids Local exhaust ventilation. PPE—chemical goggles and/or face shield Work/rest regimen. general area ventilation None identified None identified Local exhaust ventilation and general area ventilation. trichloroethylene). PPE Chemical detinning Caustic Dross smelting Dust leaching and filtration Settling and leaf filtration Dust and heat Dust None identified Evapocentrifugation None identified Electrolytic refining Acid mist Acidification and filtration Fire refining Smelting Calcining Kettle refining Acid mists Heat Combustion gases.. fumes and dust. Contaminant grease and oil are stripped from the scrap by the solvent vapour.Process equipment Dealuminization Batch mixing Exposures Sodium hydroxide Dust Engineering/administrative controls Local exhaust. The scrap can also be degreased by steam and detergent. cuttings. PPE—chemical goggles and/or face shield Local exhaust ventilation and general area ventilation. Consumer scrap consists of recycled titanium products. In this process sized scrap is treated with vapourized organic solvent (e. work/rest regimen. work/rest regimen. heat Dust. work/rest regimen. PPE Local exhaust ventilation and general area ventilation work/rest regimen. general area ventilation. turnings and borings. plank sheet. PPE Local exhaust ventilation and general area ventilation. . heat Titanium reclamation The two primary sources of titanium scrap are the home and titanium consumers. The solvent is recirculated until it can no longer has an ability to degrease. heat Dust. PPE Local exhaust ventilation and general area ventilation. The reclamation operations include: · Degreasing. Spent solvent can then be regenerated. fumes.g. PPE—chemical goggles and/or face shield Local exhaust ventilation and general area ventilation Local exhaust ventilation.

20 Engineering/administrative controls for titanium. noise Engineering/administrative controls Local exhaust and solvent recovery Face shields. safety glasses or goggles None known Local exhaust ventilation and control of noise from burners. Table 82. PPE—hearing protection PPE Casting Heat ENVIRONMENTAL ISSUES IN METAL FINISHING AND INDUSTRIAL COATINGS Stewart Forbes Metal Finishing The surface treatment of metals increases their durability and improves their appearance. The input materials include pre-treated titanium scrap and alloying materials such as aluminium. · Electrorefining. A single product may undergo more than one surface treatment—for example. palladium. aprons. Controls for exposures in titanium reclamation procedures are listed in table 82. by operation Process equipment Solvent degreasing Pickling Electrorefining Smelting Exposures Solvent Acids None known Volatile metals. an auto body panel may be phosphated. zirconium. primed and painted. This article deals with the processes used for surface treatment of metals and the methods used to reduce their environmental impact. Molten titanium is poured into moulds. tin. Electrorefining is a titanium scrap pre-treatment process which electro-refines scrap in a fused salt. Pre-treated titanium scrap and alloying agents are melted in a electric-arc vacuum furnace to form a titanium alloy. The titanium solidifies into a bar called an ingot. . molybdenum. · Smelting. · Casting. The acid treatment scrap is washed with water and dried.· Pickling. vanadium. long sleeves.20 . The acid-pickling process removes oxide scale from the degreasing operation by leaching with a solution of hydrochloric and hydrofluoric acids. columbium and chromium.

Continuous improvement is achieved by setting new priorities for action and repeating the sequence of actions. 2. processes and outputs. buffing and polishing compounds. Solvents and vapour degreasers are still in use . government and the community to effectively minimize the environmental effect of the operations. process change and internal recycling. 4. scale. Measure the results. Detailed process documentation will identify the waste streams and allow priorities to be set for waste reduction opportunities. 3. including oils. Solvents and vapour degreasing cleaning methods have been almost totally replaced by alkaline materials where the subsequent processes are wet. vapour degreasers and alkaline detergents. Society is concerned with the amount and the long-term effects of pollution entering the air. Initiate pollution prevention across all aspects of the business. water and land environment. 5. Establish root cause of the waste. using the following planning sequence: 1. Informed decisions about potential changes will encourage: · easy and practical operational improvements · process changes involving customers and suppliers · changes to less harmful activities where possible · reuse and recycling where change is not practical · using landfilling of hazardous wastes only as a last resort. Effective environmental management is established through detailed knowledge of all elements. Major processes and standard operating processes Cleaning is required because all metal finishing processes require that parts to be finished be free from organic and inorganic soils. chemicals. Set priorities for action. employees. metals. Identify waste streams. Identify and implement changes that reduce or eliminate the waste. The three basic types of cleaners in use are solvents. 6.Operating a metal finishing business requires cooperation between company management. Pollution prevention planning shifts the environmental management philosophy from reacting to problems to anticipating solutions focusing on chemical substitution.

bronze. treats the parts with dilute chromic or sulphuric acid solutions. gold. Copper or nickel electroless deposition is used in the manufacture of printed circuit boards.where parts must be clean and dry with no further wet processing. tin-lead. hydrochloric and nitric. For phosphating. Figure 82. The acids are typically sulphuric. cadmium. Electroplating involves the deposition of a thin coat of metal (zinc. an electrochemical process to thicken the oxide film on the metal surface (frequently applied to aluminium).7 Inputs and outputs for a typical electroplating line Chemical milling and etching are controlled dissolution immersion processes using chemical reagents and etchants. nickel. brass. Good management practices Important safety.1. non-silicated cleaners are typically used to clean aluminium.1-trichloroethane have been substituted for more hazardous materials in vapour degreasing (although this solvent is being phased out as an ozone depleter). followed by a weak acid immersion. health and environmental improvements can be achieved through process improvements. Less toxic materials such as 1. such as: · using counter-current rinsing and conductivity controls · increasing drainage time . copper. Non-etching. Aluminium is typically etched in caustic prior to anodizing or chemically brightened in a solution which could contain nitric. Conversion coating is used to provide a base for subsequent painting or to passivate for protection against oxidation. silver and other metals such as platinum) on a substrate (ferrous or non-ferrous). alkaline neutral and alkaline cyanide formulations (see figure 82. Passivating is accomplished through immersion in nitric acid or nitric acid with sodium dichromate. chromium. Hot-dip coatings involve the application of metal to a workpiece by immersion in molten metal (zinc or tin galvanizing of steel). parts are immersed in a hexavalent chrome solution with active organic and inorganic agents. Anodizing. Electroless plating involves a deposition of metal without electricity. Process baths include metals in solution in acid. parts are immersed in dilute phosphoric acid with other agents.7). tin. With chromating. Solvents such as terpenes are in some instances replacing volatile solvents. Alkaline cleaning cycles usually include a soak immersion followed by an anodic electroclean. phosphoric and sulphuric acids. lead.

calcium. iron.. Improving rinse water efficiency reduces the volume of bath sludges requiring treatment.e. usually spent plating solutions. written procedures. manganese. chlorine and carbonates) can be removed by using deionization. thus increasing drag-out recovery (i. Environmental planning for specific wastes Specific waste streams. can be reduced by: · Filtration. · Carbon treatment can be used to remove organic contaminants (most commonly applied in nickel plating. distillation or reverse osmosis. atmospheric evaporation. recovery of solution left on metal) · using air agitation in rinsing to increase rinsing efficiency · using plastic balls in plating tanks to reduce misting · using improved filtration on plating tanks to reduce the frequency of purification treatment · placing a curb around all process areas to contain spills · using separate treatments for recoverable metals such as nickel · installing recovery systems such as ion exchange. magnesium. Lowering the bath temperature to –3 °C crystallizes the carbonates formed in cyanide bath by the breakdown of cyanide. · Cyanide bath carbonate freezing. . which reduce the efficiency of the process.e.g.. · Purified water. The natural contaminants in water make-up and rinses (e. vacuum evaporation.· using more or better wetting agents · keeping process temperatures as high as possible to lower viscosity. Cartridge or diatomaceous earth filters can be used to remove the accumulation of solids. excessive anode current densities and the adsorption of carbon dioxide from the air and facilitates their removal. electrolytic recovery.. regular operating reviews and sound operating logs) to provide the basis for a sound environmental management structure. reverse osmosis and electrodialysis · complementing drag-out recovery systems with reductions in drag-in of contaminants and improved cleaning systems · using modern inventory controls to reduce waste and workplace hazards · applying standard procedures (i. copper electroplating and zinc and cadmium plating).

· Alkaline cleaners. · Hexavalent chrome alternatives. calcium hydroxide. · Drag-out reduction. Reducing the volume of drag-out from process baths serves to reduce the amount of valuable process chemicals that contaminates the rinse water. Hexavalent chromium can be replaced with trivalent chromium plating solutions for decorative plating. . and complex cyanides are commonly precipitated using ferrous sulphate. Hot alkaline cleaning baths can be used in place of solvent degreasing of workpieces before processing. Using non-cyanide process chemistries both eliminates a treatment step and reduces the sludge volume. Removal of metal contaminants entering the bath as impurities in anodes can be achieved through precipitation with barium cyanide. These metals can be allowed to precipitate and can be removed by continuous filtration. barium hydroxide. The viscosity of the process solution can be reduced by increasing the bath temperature. · Wetting agents. which in turn reduces the amount of sludge that is generated by a conventional metal precipitation treatment process. Waste streams containing free cyanide are typically treated using hypochlorite or chlorine to accomplish oxidation. The chemical concentration should be kept as low as possible to minimize the viscosity (for quicker draining) and the quantity of chemicals (in the film). Instead of chelators being added to process baths to control the concentration of free ions in the solution. · Non-cyanide process chemicals. Several methods of reducing drag-out include: · Process bath operating concentration. The benefits of avoiding solvent vapours and sludges often outweigh any additional operating costs. settling devices or cartridge filters to remove particulates and oil-water coalescers and by using microfiltration or ultrafiltration to remove emulsified oils. The effectiveness of alkaline cleaners can be enhanced by applying electrocurrent or ultrasonics. · Non-chelated process chemistries.· Precipitation. Chrome conversion coatings for paint pretreatments can sometimes be replaced by non-chrome conversion coatings or no-rinse chrome chemistries. The surface tension of the solution can be reduced by adding wetting agents to the process bath. · Process bath operating temperature. · Solvent degreasing. non-chelated process chemistries can be used so that it may not be necessary to keep metals in solution. grease and soils from use reaches a level which impairs the cleaning efficiency of the bath can be avoided by using skimming devices to remove free-floating oils. Having to discard alkaline cleaners when the accumulation of oil. calcium sulphate or calcium cyanide.

the thicker the film on the workpiece surface.· Workpiece positioning. · Reverse osmosis. This is an electrolytic process whereby the dissolved metals in the solution are reduced and deposited on the cathode. The faster a workpiece is removed from the process bath. Carbonates and organic contaminants should be removed to prevent accumulation of contamination that increases the viscosity of the plating bath. Atmospheric evaporators are most common. · Drag-out tanks. while most dissolved salts are retained by the membrane. Drag-out recovery of chemicals uses a variety of technologies. · Withdrawal or drainage time. · Drainage boards. Movement of the . These can be used above heated baths so that the rinse flow rate equals the evaporation rate of the tank. Rinse water Most of the hazardous waste produced in a metal finishing facility comes from waste water generated by the rinsing operations that follow cleaning and plating. This utilizes a semi-permeable membrane to produce purified water and a concentrated ionic solution. · Plating baths. High pressure is used to force the water through the membrane. By increasing rinse efficiency. First. · Ion exchange is used for chemical recovery of rinse water. The workpieces should be placed in drag-out tanks (―static rinse‖ tanks) before the standard rinsing operation. Two basic strategies improve rinsing efficiency. Blowing air at the workpiece as the workpiece rack is raised above the process tank can improve drainage and drying. a facility can significantly reduce waste water flow. · Air knives. The deposited metal is then recovered. The workpiece should be positioned on the rack so that the adhering film drains freely and does not get trapped in grooves or cavities. · Spray rinses. The spaces between process tanks should be covered with drainage boards to capture process solutions and to return them to the process bath. These include: · Evaporation. turbulence can be generated between the workpiece and the rinse water through spray rinses and rinse water agitation. and vacuum evaporators offer energy savings. This utilizes ion-permeable membranes and applied current in order to separate ionic species from the solution. · Electrowinning. · Electrodialysis.

rack or forced water or air are used. lead. Industrial Coatings The term coatings includes paints. Second. coating. varnishes. function. Coating processes There are five operations comprising most coating processes: raw materials handling and preparation. glycol ethers and alcohols. esters. surface preparation. resins. transfer efficiency and drying and curing speed determine formulations. rubbers and polymers. enamels and shellacs. Raw material handling and preparation . Industrial facilities incorporate coating operations in various production processes. wood and metal furniture and fixtures. Solvents disperse or dissolve the binders and decrease the coating viscosity and thickness. coil coating. product safety. cohesiveness and consistency and is the primary component that remains on the surface when coating is completed. Most solvents contained in a coating evaporate when the coating cures. zinc. and household appliance industries are the major industrial coatings consumers. Architectural coatings are used in buildings and building products and for decorative and protective services such as varnishes to protect wood. metal can. paint brush cleaners and allied paint products. Pigments often contain heavy metals such as cadmium. which generates volatile organic compound (VOC) emissions. coating application technologies and coating wastes are a driving force for developing pollution prevention alternatives. aromatic hydrocarbons. equipment cleaning and waste management. ketones. Cost. paint and varnish removers. Design of a coating formulation depends on the purpose of the coating application. Additives such as fillers and extenders may be added to coatings to reduce manufacturing costs and increase coating durability. environmental safety. Pigments are inorganic or organic compounds that provide coating colour and opacity and influence coating flow and durability. Most coatings are used on architectural. farm machinery. the contact time between the workpiece and the rinse water can be increased. The binder increases coating adhesiveness. Multiple rinse tanks set countercurrent in series will reduce the amount of rinse water used. chromium and cobalt. Coatings provide aesthetics. Environmental concerns associated with conventional ingredients. VOC emissions are becoming increasingly regulated because of the negative effects on human health and the environment. and corrosion and surface protection. Solvents used in coatings formulations are hazardous because many are human carcinogens and are flammable or explosive. putties. The automotive. lacquers. industrial or special products. wood fillers and sealers. The types of organic solvents used in coatings include aliphatic hydrocarbons. Liquid coatings contain pigments and additives dispersed in a liquid binder and solvent mixture. Binders include a variety of oils.

used to promote adhesion of organic coatings onto metal surfaces and retard corrosion. Coating The coating operation involves transferring the coating to the surface and curing the coating on the surface. and the most common technique. Common preparation operations include degreasing. Phosphate coatings are applied by immersing or spraying metal surfaces with zinc. is conducted on surfaces that require recoating. mixing operations. iron or manganese phosphate solution. The most common chemical coating removal method is solvent stripping. These solutions usually contain phenol. Phosphating is a surface finishing process similar to electroplating. Most coating technologies fall into 1 of 5 basic categories: dip coating. generating either used filters or wastewater from air scrubbing systems. amount of soil. whether manual or through a piped system. spray coating. semi-aqueous cleaning or aliphatic hydrocarbon cleaning to remove organic soil. . For metal finishing purposes. Coating removal. other than cleaning. then removal of the coating and recoating adds to waste generation. The most common preparation operation for metal surfaces. is phosphate coating. grease. consisting of a series of process chemical and rinse baths in which parts are immersed to achieve the desired surface preparation. abrasive cleaning or flame cleaning are used to remove mill scale and rust. A final water wash to remove the chemicals can generate large quantities of wastewater. chemical or mechanical. repair or inspection. Monitoring and handling procedures and practices are needed to minimize the generation of wastes from spoilage. a dry operation that uses compressed air to propel a blasting medium against the surface to remove the coating. off specification and improper preparation that can result from excessive thinning and consequent wastage. the coating to be applied and the surface finish required. precoating or phosphating and coating removal. Air-atomized spray coatings are usually conducted in a controlled environment because of solvent emissions and overspray. must be scheduled to avoid spoilage. Transfer. oil and grease. flow coating. air-atomized spray coating using solvent-based coatings. degreasing involves solvent wiping. Surface preparation The type of surface preparation technique used depends on the surface being coated—previous preparation. aqueous alkaline cleaning. resulting in poor coating. If the surface preparation is inadequate. dirt.Raw material handling and preparation involves inventory storage. Abrasive blasting is the common mechanical process. roll coating. methylene chloride and an organic acid to dissolve the coating from the coated surface. thinning and adjusting of coatings and raw material transfer through the facility. Surface preparation operations affect the quantity of waste from the specific preparation process. cold cleaning or vapour degreasing with halogenated solvents. Overspray control devices are fabric filters or water walls. See the article ―Surface treatment of metals‖ in this chapter. Acid pickling.

Environmental and health concerns. This creates significant amounts of hazardous waste. . Water-based liquids are usually treated onsite prior to discharge to publicly owned treatment systems. Equipment cleaning Equipment cleaning is a necessary. Solid waste includes empty coating containers. Compared to solvent-based coatings. The procedures and practices used will determine the level of waste generated from these activities. · Water-based coatings using water and an organic solvent mixture as the carrier with water used as the base. tough. consisting of finely pulverized pigment and resin particles. baking or exposure to an electron beam or infrared or ultraviolet light. overspray. water-based coatings generate between 80 and 95% less VOC emissions and spent solvents than conventional low-solid solvent-based coatings. spent filters and abrasive materials. spills and spent cleaning solutions. Curing mechanisms include: drying. Consequently. routine maintenance operation in coating processes. Alternative coating formulations include: · High-solid coatings. · Powder coatings containing no organic solvent. containing twice the amount of pigment and resin in the same volume of solvent as conventional coatings. Coating equipment must be cleaned between product changes and after process shutdowns. curing operations are equipped with air pollution control devices to prevent VOC emissions and for safety control to prevent explosions. Piping requires flushing with solvent in batches until clean. Equipment cleaning for solvent-based coatings has traditionally been conducted manually with organic solvents to remove coatings from process equipment. coating sludge from overspray and equipment cleaning. Application lowers VOC emissions between 62 and 85% compared to conventional low-solid solvent-based coatings because the solvent content is reduced. off-specification or excess coating or surface preparation materials. dry coating and cleaning rags. adherent surface. Liquid wastes include waste water from surface preparation. Onsite closed-loop recycling is becoming more popular for spent solvents as disposal costs rise. Curing generates significant VOCs from solvent-based coatings and poses a potential for explosion if the solvent concentrations rise above the lower explosive limit. Waste management Several waste streams are generated by coating processes. increased regulations affecting conventional coating formulations. high solvent costs and expensive hazardous waste disposal have created a demand for alternative coating formulations that contain less hazardous constituents and generate less waste when applied.Curing is performed to convert the coating binder into a hard. overspray control or equipment cleaning. particularly if halogenated solvents are used for cleaning. They are either thermoplastic (high molecular weight resin for thick coatings) or thermosetting (low molecular weight compounds that form a thin layer before chemically crosslinking) powders.

American National Standards Institute (ANSI). 1992. and DE Griffith. 1984. Scand J Work Environ Health 12:32–39. Ann NY Acad Sci 643:397–403. Thomas. 1991. AJ and WT Davis (eds. The persistence of an ancient disease. Silicosis in a grey iron foundry. .VOC emissions are generated by all conventional coating processes that use solvent-based coatings. 1985. Lyon: IARC. A Dybunico. PR and D Clarke. 1996. Monographs on the Evaluation of Carcinogenic Risks to Humans. Landrigan. Johnson A. Respiratory abnormalities amongst workers in iron and steel industry. D and A Taylor. DC: EPA. 1992 Vibration white finger and Dupuytren’s contracture: Are they related? Occup Med 42(3):155–158. Kronenberg RS. 1986. Cincinatti. requiring control devices such as carbon adsorption units. 1995. 1976. and D Enarson. OH: NIOSH.6-1976. Mercury in environmental and biological samples from a gold mining area in the Amazon Region of Brazil. condensers or thermal catalytic oxidizers. EPA/310-R-95-010. CY Moira. RF Dodson. International Association for Research on Cancer (IARC).). FA Lewis. 22nd ed. and RW Hornung. F Cheng. Industrial Ventilation: A Manual of Recommended Practice. 34. 1992. Palheta. Profile of the Nonferrous Metals Industry. 1995. Cincinnati. REFERENCES Buonicore. OTHER RELEVANT READINGS American Conference of Government Industrial Hygienists (ACGIH) Committee on Industrial Ventilation. ANSI B11. Science of the Total Environment 168:63-69. JC Levin. New York: Van Nostrand Reinhold/Air and Waste Management Association. JGN Garcia. OH: ACGIH. L MacLean. Vol. Safety Requirements for the Construction. Brit J Ind Med 42:94–100. National Institute for Occupational Safety and Health (NIOSH). Criteria for a Recommended Standard: Occupational Exposures to Metalworking Fluids. Environmental Protection Agency (EPA). and Use of Lathes. Air Pollution Engineering Manual. E Atkins. Washington. Asbestos-related disease in employees of a steel mill and a glass bottle manufacturing plant. New York: ANSI. PJ. MG Cherniack. LR Catlett. Care.

—. 1988a. The Use, Care, and Protection of Abrasive Wheels. ANSI B7.1-1988. New York: ANSI. —.1988b. Safety in Welding and Cutting. ANSI Z49.1-1988. New York: ANSI. American Petroleum Institute (API). 1971. Chemistry and Petroleum for Classroom Use in Chemistry Courses. Washington, DC: API. —. 1980. Facts about Oil. Manual 4200. Washington, DC: API. —. 1984. Safe Operation of Inland Bulk Plants. Publication 2008. Washington, DC: API. Antoni, H. 1978. Massnahmen zu höherer Sicherheit beim Spannen mit Backenfuttern [Measures to increase safety in gripping with jaw chucks]. Zeitschrift für industrielle Fertigung 10:611–615. Burgess, WA. 1995. Recognition of Health Hazards in Industry, 2nd edition. New York: John Wiley & Sons. Exxon Company. 1987. Encyclopedia for the User of Petroleum Products. Houston, TX: Exxon Company, USA, Marketing Technical Services. Goldsmith, AH, KW Vorpahl, KA French, PT Jordan, and NB Jurinski. 1976. Health hazards from oil, soot and metals at a hot forging operation. Am Ind Hyg Assoc J 37:217–226. Gulf Publishing Company. 1964. Petroleum Marketing and Transportation, 1964. Houston TX: Gulf Publishing Company. Harten, GA. 1976. Een nieuwe, ergonomisch verbeterde draaibank [A new, ergonomically improved lathe]. Tijdschrift voor sociale geneeskunde (Amstelveen) 54(17):575–578. Kusiak, RA, J Springer, AC Ritchie, and J Muller. 1991. Carcinoma of the lung in Ontario gold miners: Possible aetiological factors. Brit J Ind Med 48(12):808-817. Mobil Oil Corporation. 1990. Handling, Storing and Dispensing Industrial Lubricants. Mobil Technical Bulletin. Fairfax, VA: Mobil Oil Corporation. National Institute for Occupational Safety and Health (NIOSH). 1975. Ventilation Requirements for Grinding, Buffing and Polishing Operations. NIOSH Publ. No. 75-105. Cincinnati, OH: NIOSH. National Safety Council. 1995. Petroleum Section Safety and Health Fact Sheets, 1988-95. Itasca, IL: National Safety Council. Occupational Safety and Health Administration (OSHA). 1979. Prudent Practices for Controlling Lead Exposure in the Secondary Lead Smelting Industry: A Guide for Employers and Employees. Washington, DC: OSHA.

—. 1982. Cooperative Assessment Program Manual for the Secondary Lead Smelting Industry. Washington, DC: OSHA. —. 1984. Cooperative Assessment Program Manual for the Battery Manufacturing Industry. Washington, DC: OSHA. Ontario Metal Finishing Industry Pollution Prevention Project. 1995. Metal Finishing Pollution Prevention Guide. Ottawa: Environment Canada, Water Technology International, Sheridan Environmental Technology Institute. Simonato, L, JJ Moulin, B Javeland, G Ferro, P Wild, R Winkelmann, and R Saracci. 1994. A retrospective mortality study of workers exposed to arsenic in a gold mine and refinery in France. Am J Ind Med 25:652-633.

Part XIII - Manufacturing Industries

Français

Ladle refining
Dr. Dmitri Kopeliovich

 

Vacuum ladle degassing o Recirculation Degassing (RH) o Recirculation Degassing with oxygen top lance (RH-OB) o Ladle Degassing (VD, Tank Degassing) o Vacuum Oxygen Decarburization (VOD) Ladle Furnace (LF) Ladle desulfurization by injection of active agents o Powder injection o Cored wire injection Ladle-to-mold degassing

Vacuum ladle degassing Methods of vacuum ladle degassing utilize the reaction of deoxidation by carbon dissolved in steel according to the equation: [C] + [O] = {CO} where: [C] and [O] - carbon and oxygen dissolved in liquid steel; {CO} - gaseous carbon monoxide. Vacuum treatment of molten steel decreases the partial pressure of CO, which results in shifting equilibrium of the reaction of carbon oxidation. Bubbles of carbon monoxide form in the liquid steel, float up and then they are removed by the vacuum system. In addition to deoxidation vacuum treatment helps to remove Hydrogen dissolved in liquid steel. Hydrogen diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump. Movement of the molten steel caused by CO bubbles also results in refining the steel from nonmetallic inclusions, which agglomerate, float up and are absorbed by the slag. CO bubbles also favor the process of floating and removal of nitride inclusions and gaseous Nitrogen. Steels refined in vacuum are characterized by homogeneous structure, low content of nonmetallic inclusions and low gas porosity. Vacuum degassing methods are used for manufacturing large steel ingots, rails, ball bearings and other high quality steels. Vacuum ladle degassing methods:

-Oxygen removal (deoxidation). -Non-metallic inclusions removal. The circulation rate may reach 150-200 t/min. through which alloying elements or/and desulfurization slag may be added. The snorkels of the vacuum chamber are immersed into the ladle with molten steel. -Temperature and chemical homogenizing. Through the second snorkel (down-leg) the molten steel flows down back to the ladle producing circulation. Liquid metal fills the chamber to a level determined by the atmospheric pressure (4. The recirculation degassing vacuum chambers are usually equipped with addition hoppers. . Recirculation Degassing (RH) Recirculation degassing unit uses a vacuum chamber having two snorkels connected to the chamber bottom.2ft/1. -Sulfur removal (desulfurization). -Precise alloying. One of the snorkels is equipped with pipes supplying Argon through its refractory lining.3m). Argon bubbles floating up in one of the snorkels (up-leg) force the melt to rise in the snorkel. -Carbon removal (decarburization). Benefits of Recirculation Degassing (RH): -Hydrogen removal (degassing).

 Ladle Degassing (VD. Oxygen intensifies the reaction [C] + [O] = {CO} resulting in fast and effective decarburization. -Sulfur removal (desulfurization). Oxidation reactions have also heating effect therefore the treated metal may be heated to a required temperature without any additional energy source. Tank Degassing) . -Precise alloying. -Phosphorus removal (dephosporization). Recirculation Degassing with oxygen top lance (RH-OB) In this method a conventional Recirculation degassing (RH) vessel (chamber) is equipped with a vertical water cooled lance for blowing oxygen on the molten steel surface. -Non-metallic inclusions removal. -Fast carbon removal (decarburization). Benefits of Recirculation degassing with oxygen top lance (RH-OB): -Hydrogen removal (degassing). -Reheating. -Temperature and chemical homogenizing. Oxygen also oxidizes phosphorus like in Basic Oxygen Process (BOP) or in oxidizing slag stage in Electric-arc furnace.

. which is additionally intensified by argon blown through the bottom porous plug. Argon and CO bubbles also favor the process of floating and removal of nitride inclusions and gaseous nitrogen. Desulfurizing slags possessing high sulfur solubility are used in this process. -Temperature and chemical homogenizing.In the Tank Degassing method the ladle with molten steel is placed into a vacuum chamber. -Deep sulfur removal (desulfurization). The hopper is used for adding alloying elements and/or slag components. The ladle is equipped with a porous refractory plug mounted in the ladle bottom. Through the plug argon is supplied during vacuum treatment. -Oxygen removal (deoxidation). -Non-metallic inclusions (oxides and nitrides) removal. There is an addition hopper with vacuum lock on the chamber cover. -Precise alloying. Benefits of Ladle Degassing (VD. The reaction [C] + [O] = {CO} starting in the steel under vacuum conditions causes stirring. Intensive stirring of the melt and the slag results in deep desulfurization of the steel. -Carbon removal (decarburization). Tank Degassing): -Hydrogen removal (degassing).

-Sulfur removal (desulfurization). Stirring of the melt and the slag caused by argon blown through the porous bottom plug results in deep desulfurization of the steel. . -Low losses of chromium in treatment of stainless steels. Vacuum Oxygen Decarburization (VOD) In this method a conventional Ladle Degassing (VD. Benefits of Vacuum Oxygen Decarburization (VOD): -Deep carbon removal (decarburization). which is the main constituent of stainless steels. Oxidation reactions have also heating effect therefore the treated metal may be heated to a required temperature without any additional energy source. Then a Desulfurizing slag is added to the molten steel surface. -Hydrogen removal (degassing). VOD process allows to decarburize the steel with minor chromium losses. After having the decarburization (oxidation) stage completed deoxidizers are added to the steel in order to remove excessive oxygen. Vacuum Oxygen Decarburization (VOD) method is used for manufacturing Stainless steels. Tank Degassing) chamber is equipped with a vertical water cooled lance for blowing oxygen on the molten steel surface. Oxidation of liquid steel components under vacuum differs from that at normal pressure: oxygen is consumed mainly by the reaction [C] + [O] = {CO} rather than by oxidation of chromium.

-Non-metallic inclusions (oxides and nitrides) removal. to top Ladle Furnace (LF) Molten steel in a ladle may be treated (refined) in a device called Ladle Furnace (LF). The ladle is transported to the Ladle Furnace stand where it is placed under a cover equipped with three graphite electrodes connected to a three-phase arc transformer. The graphite .-Precise alloying. Fumes formed during the operation are extracted through the cover. -Temperature and chemical homogenizing. which is connected to the argon supply pipe at the Ladle Furnace stand. -Reheating. The ladle bottom has a porous refractory plug. Molten steel treated in Ladle Furnace is covered by a layer of desulfurizing slag. The LF stand is also equipped with an addition hopper mounted on the cover and a lance for injection of desulfurizing agents.

Besides refining operations Ladle Furnace (LF) may serve as a buffer station before Continuous casting. A ladle with deoxidized (killed) molten steel is transported to the injection stand where it is placed under a cover. Ladle Furnace process is used for refining a wide variety of steels. CaSi. Stirring also provides thermal and chemical homogenization of the melt. CaF2+CaO) to a molten steel is the most effective method of sulfur removal. Argon bubbles produce stirring of the molten steel and the slag promoting desulfurization. in which degassing (hydrogen removal) is not required. chemical homogenization and desulfurization of the steel by the slag. Controllable reheating by electric power. Alloying elements and/or slag components may be added through the addition hopper. Mg. Benefits of Ladle Furnace (LF):      Deep sulfur removal (desulfurization). Stirring results in distribution of heat produced by the arcs. Temperature and chemical homogenizing. If deep desulfurization is required active desulfurizing agents are injected into the melt through the injection lance or in form of cored wire. During the treatment process argon is blown through the bottom porous plug providing continuous metal stirring. Desulfurization agents are injected in argon stream. Injection methods usually combine supply of a disperse desulfurizing agent (powder) with stirring by argon blowing. through which the injection lance may lower and immerse into the melt. The arcs are capable to heat the steel at the rate about 5°F/min (3°C/min). Steel treated in the stand is covered by a layer of desulfurizing slag having high solubility of sulfur and capable to absorb sulfides formed as a result of active agents injection. When the desulfurizing agents are injected into molten steel in form of a cored wire containing . to top Ladle desulfurization by injection of active agents Injection of desulfurizing agents (Ca.electrodes are submerged into the slag. Non-metallic inclusions removal. Alloying. CaC2. which protects the ladle lining from overheating produced by the electric arcs.

0002%).powder of desulfurizing agent stirring by argon bubbling from the porous plug mounted in the ladle bottom is used. . Temperature and chemical homogenizing. Injection of desulfurizing agents allows to achieve ultra-low concentrations of sulfur in steel (0. Fumes formed during the operation are extracted through the cover. Non-metallic inclusions removal. Benefits of Ladle desulfurization by injection of active agents:    Deep sulfur removal (desulfurization).

to top Ladle-to-mold degassing .

at which the melt stream ―opens‖ as a result of CO bubbles formation.Ladle-to-mold degassing is a vacuum degassing method. . The tundish is continuously filled with the melt poured from the ladle. The steel stream ―boils‖ when it is falling to the mold cavity in vacuum due to the deoxidation reaction [C] + [O] = {CO}. in which the mold is placed in a vacuum chamber. The molten steel is poured from a tundish attached to the cover of the chamber. Intensity of the deoxidation and degassing during Ladle-to-mold pouring is indicated by the angle. Hydrogen dissolved in steel diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump.

Dmitri Kopeliovich Electric Arc Furnace (EAF) is a steel making furnace. About 33% of the crude steel in the world is made in the Electric Arc Furnaces (EAF).     Structure of an Electric Arc Furnace Refractory lining of an Electric Arc Furnace Chemical and physical processes in an Electric Arc Furnace Operation of an Electric Arc Furnace Structure of an Electric Arc Furnace . Three-phase AC Electric Arc Furnaces with graphite electrodes are commonly used in steel making. The main advantage of the Electric Arc Furnaces over the Basic Oxygen Furnaces (BOF) is their capability to treat charges containing up to 100% of scrap. in which steel scrap is heated and melted by heat of electric arcs striking between the furnace electrodes and the metal bath. Capacity of Electric Arc Furnace may reach 400 t. Two kinds of electric current may be used in Electric Arc Furnaces: direct (DC) and alternating (AC).Electric Arc Furnace (EAF) Dr.

The electrode and the scrap form the star connection of three-phase current. The scrap arranged in the charge basket is transferred to the furnace by a crane and then dropped into the shell. The arc during this period is unstable. . The scrap is charged commonly from the furnace top. The furnace consists of a spherical hearth (bottom). The charge door is also used for removing the slag (de-slagging). in which the scrap is common junction. The roof has three holes for consumable graphite electrodes held by a clamping mechanism.The scheme of a Electric Arc Furnace (EAF) is presented in the picture. The roof with the electrodes is swung aside before the scrap charging. The molten metal flows down to the furnace bottom. The water-cooled electrode holders serve also as contacts for transmitting electric current supplied by water-cooled cables (tubes). The electrodes descend melting the charge and penetrating into the scrap forming bores. cylindrical shell and a swinging watercooled dome-shaped roof. When the bricks are heated the bonding material is coked and turns into a carbon network binding the refractory grains. The electrodes are lifting together with the melt level. Most of scrap (85%) melt during this period. preventing wetting by the slag and protecting the lining the from erosion and chemical attack of the molten metal and slag. The mechanism provides independent lifting and lowering of each electrode. to top Chemical and physical processes in an Electric Arc Furnace Melting Melting process starts at low voltage (short arc) between the electrodes and the scrap. Temperature of the arc reaches 6300ºF (3500ºC). The charge door. is located on the front side of the furnace shell. Fused magnesite grains and flake graphite are used as raw materials. The furnace is mounted on a tilting mechanism for tapping the molten steel through a tap hole with a pour spout located on the back side of the shell. to top Refractory lining of an Electric Arc Furnace Refractory linings of Electric Arc Furnaces are made generally of resin-bonded magnesia-carbon bricks. through which the slag components and alloying additives are charged. In order to improve the arc stability small pieces of the scrap are placed in the upper layer of the charge. When the electrodes reach the liquid bath the arc becomes stable and the voltage may be increased (long arc).

The oxidizing slag enriched with phosphorous and other oxides formed during this period is removed from the furnace to a slag pot (de-slagging). Basic oxidizing slag composed of lime (CaO) and ion ore (FeO) is used during the oxidizing period. Gaseous products CO and CO2 are removed by the exhausting system. silicon and manganese: [C] + [O] = {CO} [Si] + {O2} = (SiO2) [Mn] + 1/2{O2} = (MnO) 2[P] + 5/2{O2} = (P2O5) Carbon monoxide partially burns in the atmosphere: {CO} + {O2} = {CO2} The formed oxides are absorbed by the slag. silicon and manganese oxidize. The process is similar to that in Basic Oxygen Furnace. Oxidizing potential of the atmosphere is characterized by the post-combustion ratio: {CO2}/({CO2}+{CO}). curly brackets {} . The function of this slag is refining of the steel from sulfur and absorption of oxides.Oxidizing stage At this stage excessive carbon. CO bubbles floating up through the melt result in refining of the steel from non-metallic inclusions and hydrogen removal. Reducing stage New slag composed mainly of lime (CaO). CaF2 (as slag fluidizer) is added at this stage for formation of basic reducing conditions.in gas) (FeO) = [Fe] + [O] Oxygen dissolved in the melt oxidizes carbon.signify solution in steel. Iron oxide causes increase of Oxygen content in the molten steel according to the reaction: (square brackets [ ] . round brackets ( ) . Gaseous oxygen may be blown into the melt for additional oxidizing. formed as a result of deoxidation (‖killing‖). .in slag. phosphorous. phosphorous.

In many cases the processes of ―killing‖ (deoxidation). Steel contains lower (compared to pig iron) quantities of impurities like phosphorous. Alloying. Alloying elements (Cr. to top Operation of an Electric Arc Furnace             Scrap charging. alloying and final heating are performed outside of the furnace . Oxidation of C. Oxidizing slag formation. Mn.The excessive oxygen dissolved in the melt during oxidizing period is removed by metallic deoxidizers Mn. containing up to 2% of carbon (usually up to 1%). Sampling and chemical analysis of the melt.) are added after deoxidation. Mo. De-slagging. Steel making (introduction) Dr. Basic slag formation. Si. Tapping the steel. Al. etc. Melting. Ni. Sampling and temperature measurement. V. sulfur and silicon. Si. Al: [Mn] + [O] = (MnO) [Si] + 2[O] = (SiO2) 2[Al] + 3[O] = (Al2O3) Basic reducing slag is favorable for desulfurization in accordance to the reaction: [S] + (CaO) = (CaS) + [O] Oxide and sulfide non-metallic inclusions are absorbed by the slag. P. Refractory lining maintenance.Ladle refining. desulfurization. Deoxidizing (‖killing‖). Dmitri Kopeliovich Steel is an alloy of iron. .

The main steel making methods are:    Basic Oxygen Process (BOP) Electric-arc furnace Ladle refining (ladle metallurgy. The furnace is capable to rotate about its horizontal axis on trunnions. silicon and phosphorous. secondary refining) Basic Oxygen Process (BOP) The Basic Oxygen Process is the most powerful and effective method of steel manufacturing.Steel is produced from pig iron by processes. involving reducing the amounts of carbon. basic oxygen converter) is presented in the picture. Typical basic oxygen converter has a vertical steel shell lined with refractory lining. . The scheme of the Basic Oxygen Furnace (BOF) (basic oxygen furnace.

The Basic Oxygen is equipped with the water cooled oxygen lance for blowing oxygen into the melt. The forming oxides and sulfur are absorbed by the slag. Charging fluxes. The basic oxygen converter uses no additional fuel. The oxygen converter has a capacity up to 400 t and production cycle of about 40 min. manganese and phosphorous) serve as fuel.This rotation is necessary for charging raw materials and fluxes. Oxygen blowing. The iron impurities oxidize. The steel making process in the oxygen converter consists of:        Charging steel scrap. to top Electric-arc furnace . Sampling and temperature measurement Tapping the steel to a ladle. Pouring liquid pig iron into the furnace. silicon. necessary for the process. sampling the melt and pouring the steel and the slag out of the furnace. De-slagging. evolving heat. The pig iron impurities (carbon.

The oxides are absorbed into the slag. silicon and manganese. The steel making process in the electric-arc furnace consists of:    Charging scrap metal. produced by the arcs. formed as a result of deoxidation. By the end of the stage the slag is removed.The electric-arc furnace employs three vertical graphite electrodes for producing arcs. causes oxidizing phosphorous. striking on to the charge and heating it to the required temperature. limestone Lowering the electrodes and starting the power (melting) Oxidizing stage At this stage the heat.   De-slagging Reducing stage New fluxes (lime and anthracite) are added at this stage for formation of basic reducing slag.  Tapping . The function of this slag is refining of the steel from sulfur and absorption of oxides. As the electric-arc furnace utilizes the external origin of energy (electric current). it is capable to melt up to 100% of steel scrap. pig iron.

Sulfur refining (desulfurization) in the ladle metallurgy is performed by addition of fluxes (CaO. deoxidation and others. performed in the ladle prior to casting with the purposes of desulfurization. In one of the tubes argon is injected. Vacuum causes proceeding chemical reaction within the molten steel: [C] + [O] = {CO} This reaction results in reduction of the quantity of oxide inclusions. cause steel circulation through the vacuum vessel. Basic Oxygen Furnace (BOF) . to top Ladle refining (ladle metallurgy. Easy temperature control. Ladle refining may be carried out at atmospheric pressure. gas purging and stirring. which consists of a vacuum vessel with two tubes (snorkels). temperature and chemical homogenization. CaF2 and others) into the ladle and stirring the steel together with the slag. In the production of high quality steel the operation of vacuum treatment in ladle is widely used. Additions of fluxes in the vacuum vessel permits conducting desulfurization treatment by this method. secondary refining) Ladle refining is post steel making technological operations. at vacuum. Argon bubbles. moving upwards. Precise alloying. immersed in the steel. diffusing into the CO phase. The bubbles of carbon oxide remove Hydrogen. absorbing sulfur. Deep desulfurization. degassing. Lining maintenance The advantages of the electric-arc furnace are as follows:     Unlimited scrap quantity may be melt. An example of ladle refining method is Recirculation Degassing (RH) vacuum degasser. may involve heating.

Dr. Basic Oxygen Converter) is the most powerful and effective steel making method. About 67% of the crude steel in the world is made in the Basic Oxygen Furnaces (BOF). Typical basic oxygen furnace has a vertical vessel lined with refractory lining. The Basic Oxygen Process (Basic Oxygen Furnace.     Furnace structure Refractory lining Chemical and physical processes Operation Structure of a Basic Oxygen Furnace The scheme of a Basic Oxygen Furnace (BOF) is presented in the picture. in which molten pig iron and steel scrap convert into steel due to oxidizing action of oxygen blown into the melt under a basic slag. Dmitri Kopeliovich Basic Oxygen Furnace (BOF) is a steel making furnace. Only 8-12% of the furnace volume is filled with the treated molten metal. Basic Oxygen Steelmaking. The bath depth is .

The oxygen pressure is 150-220 psi (1-1. tar) is coked and turns into a carbon network binding the refractory grains.projecting residual magnesia saturated slag to the lining walls by Nitrogen blown through the lance. Repair the damaged zones of the lining by gunning refractory materials. The vessel consists of three parts: spherical bottom.about 4-6. Oxygen flow commonly reaches 200-280 ft3/(min*t) (6-8 m3/(min*t)). Refractory bricks for lining basic oxygen furnaces are made of either resin bonded magnesite or tar bonded mixtures of magnesite (MgO) and burnt lime (CaO). The tuyeres are cooled by either hydrocarbon gas (propane. The vessel is attached to a supporting ring equipped with trunnions. preventing wetting by the slag and protecting the lining the from chemical attack of the molten metal.2-1. The ratio between the height and diameter of the furnace is 1.5.5 ft (1. This rotation (tilting) is necessary for charging raw materials. The following measures allows to prolong the service life of the lining:     Control of the content of aggressive oxidizing oxide FeO in the slags at low level. cylindrical shell and upper cone. The top blown basic oxygen furnace is equipped with the water cooled oxygen for blowing oxygen into the melt through 4-6 nozzles. The bonding material (resin.2-1. methane) or oil supplied to the outer jacket of the tube. Addition of MgO to the slags.9 m). The converter is capable to rotate about its horizontal axis on trunnions driven by electric motors. Performing ―slag splashes‖ . to top Chemical and physical processes in a Basic Oxygen Furnace . Service life of oxygen lance is about 400 heats. The supporting ring provides stable position of the vessel during oxygen blowing. The bottom blown basic oxygen furnace is equipped with 15-20 tuyeres for injection of oxygen (or oxygen with lime powder). The typical capacity of the Basic Oxygen Furnace is 250-400 t. Properly maintained lining may serve 20000 heats. sampling the melt and pouring the steel out of the converter.5 MPa). The lining wear is fastest in the zone of contact with the oxidizing slag (slag line). to top Refractory lining of a Basic Oxygen Furnace The refractory lining of basic oxygen furnaces work in severe conditions of high temperature and oxidizing atmosphere.

in gas) 1/2{O2} = [O] [Fe] + 1/2{O2} = (FeO) [Si] + {O2} = (SiO2) [Mn] + 1/2{O2} = (MnO) 2[P] + 5/2{O2} = (P2O5) [C] + 1/2{O2} = {CO} {CO} + 1/2{O2} = {CO2} Most oxides are absorbed by the slag. Pouring molten pig iron from blast furnace. Duration of the blowing is about 20 min. Gaseous products CO and CO2 are transferred to the atmosphere and removed by the exhausting system. Charging fluxes. Oxidizing potential of the atmosphere is characterized by the post-combustion ratio: {CO2}/({CO2}+{CO}). slag-metal). The most popular method of desulfurization is removal of sulfur from molten steel to the basic reducing slag. Sampling. silicon. However the slag formed in the Basic Oxygen Furnace is oxidizing (not reducing) therefore maximum value of distribution coefficient of sulfur in the process is about 10. Temperature measurements (by disposable thermocouple) and taking samples for chemical analysis are made through the upper cone in tilted position of the furnace. Iron and its impurities oxidize evolving heat necessary for the process. to top Operation of a Basic Oxygen Furnace      Charging steel scrap (25-30% of the total charge weight). gas-slag. Starting oxygen blowing. Basic Oxygen Process has limiting ability for desulfurization.signify solution in steel. round brackets ( ) .The basic oxygen furnace uses no additional fuel. . Finally the reactions may be presented as follows: (square brackets [ ] .in slag. curly brackets {} . which may be achieved in the slags containing high concentrations of CaO. The pig iron impurities (carbon. Oxidation of the molten metal and the slag is complicated process proceeding in several stages and occurring simultaneously on the boundaries between different phases (gas-metal. manganese and phosphorous) serve as fuel.

float up and are absorbed by the slag. {CO} . Tank Degassing) o Vacuum Oxygen Decarburization (VOD) Ladle Furnace (LF) Ladle desulfurization by injection of active agents o Powder injection o Cored wire injection Ladle-to-mold degassing Vacuum ladle degassing Methods of vacuum ladle degassing utilize the reaction of deoxidation by carbon dissolved in steel according to the equation: [C] + [O] = {CO} where: [C] and [O] .carbon and oxygen dissolved in liquid steel. which results in shifting equilibrium of the reaction of carbon oxidation. CO bubbles also favor the process of floating and removal of nitride inclusions and gaseous Nitrogen. which agglomerate. slag detectors) prevent penetration (carry-over) of the slag into the ladle. Bubbles of carbon monoxide form in the liquid steel. De-slagging . float up and then they are removed by the vacuum system.gaseous carbon monoxide. Hydrogen diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump. Vacuum treatment of molten steel decreases the partial pressure of CO. Ladle refining Dr.pouring the steel to a ladle. Dmitri Kopeliovich     Vacuum ladle degassing o Recirculation Degassing (RH) o Recirculation Degassing with oxygen top lance (RH-OB) o Ladle Degassing (VD. In addition to deoxidation vacuum treatment helps to remove Hydrogen dissolved in liquid steel.  Tapping . The furnace is turned upside down in the direction opposite to the tapping hole. Movement of the molten steel caused by CO bubbles also results in refining the steel from nonmetallic inclusions. . The Basic Oxygen Furnace has a capacity up to 400 t and production cycle (tap-to-tap) of about 40 min.pouring the residual slag into the slag pot. Special devices (plugs.

ball bearings and other high quality steels. Argon bubbles floating up in one of the snorkels (up-leg) force the melt to rise in the snorkel. Through the second snorkel (down-leg) the molten steel flows down back to the ladle producing circulation.Steels refined in vacuum are characterized by homogeneous structure.3m). One of the snorkels is equipped with pipes supplying Argon through its refractory lining. Benefits of Recirculation Degassing (RH): . The circulation rate may reach 150-200 t/min.2ft/1. Vacuum ladle degassing methods:  Recirculation Degassing (RH) Recirculation degassing unit uses a vacuum chamber having two snorkels connected to the chamber bottom. The recirculation degassing vacuum chambers are usually equipped with addition hoppers. The snorkels of the vacuum chamber are immersed into the ladle with molten steel. through which alloying elements or/and desulfurization slag may be added. Vacuum degassing methods are used for manufacturing large steel ingots. Liquid metal fills the chamber to a level determined by the atmospheric pressure (4. low content of nonmetallic inclusions and low gas porosity. rails.

Oxygen also oxidizes phosphorus like in Basic Oxygen Process (BOP) or in oxidizing slag stage in Electric-arc furnace. -Fast carbon removal (decarburization). Oxidation reactions have also heating effect therefore the treated metal may be heated to a required temperature without any additional energy source. -Non-metallic inclusions removal. Oxygen intensifies the reaction [C] + [O] = {CO} resulting in fast and effective decarburization. -Oxygen removal (deoxidation). -Precise alloying.  Recirculation Degassing with oxygen top lance (RH-OB) In this method a conventional Recirculation degassing (RH) vessel (chamber) is equipped with a vertical water cooled lance for blowing oxygen on the molten steel surface. -Sulfur removal (desulfurization). -Temperature and chemical homogenizing. . Benefits of Recirculation degassing with oxygen top lance (RH-OB): -Hydrogen removal (degassing).-Hydrogen removal (degassing). -Carbon removal (decarburization).

There is an addition hopper with vacuum lock on the chamber cover.-Phosphorus removal (dephosporization). Intensive stirring of the melt and the slag results in deep desulfurization of the steel. The reaction [C] + [O] = {CO} starting in the steel under vacuum conditions causes stirring. Through the plug argon is supplied during vacuum treatment. -Non-metallic inclusions removal. Tank Degassing) In the Tank Degassing method the ladle with molten steel is placed into a vacuum chamber. -Precise alloying. -Reheating. Desulfurizing slags possessing high sulfur solubility are used in this process. -Temperature and chemical homogenizing.  Ladle Degassing (VD. Benefits of Ladle Degassing (VD. The ladle is equipped with a porous refractory plug mounted in the ladle bottom. -Sulfur removal (desulfurization). Tank Degassing): . Argon and CO bubbles also favor the process of floating and removal of nitride inclusions and gaseous nitrogen. The hopper is used for adding alloying elements and/or slag components. which is additionally intensified by argon blown through the bottom porous plug.

-Hydrogen removal (degassing).  Vacuum Oxygen Decarburization (VOD) In this method a conventional Ladle Degassing (VD. VOD process allows to decarburize the steel with minor chromium losses. Oxidation reactions have also heating effect therefore the treated metal may be heated to a required temperature without any additional energy source. After having the decarburization (oxidation) stage completed deoxidizers are added to the steel in order to remove excessive oxygen. -Non-metallic inclusions (oxides and nitrides) removal. -Carbon removal (decarburization). Tank Degassing) chamber is equipped with a vertical water cooled lance for blowing oxygen on the molten steel surface. Oxidation of liquid steel components under vacuum differs from that at normal pressure: oxygen is consumed mainly by the reaction [C] + [O] = {CO} rather than by oxidation of chromium. -Oxygen removal (deoxidation). -Deep sulfur removal (desulfurization). -Temperature and chemical homogenizing. Vacuum Oxygen Decarburization (VOD) method is used for manufacturing Stainless steels. which is the main constituent of stainless steels. Then a Desulfurizing slag is added to the molten steel . -Precise alloying.

-Sulfur removal (desulfurization).surface. -Reheating. . to top Ladle Furnace (LF) Molten steel in a ladle may be treated (refined) in a device called Ladle Furnace (LF). -Precise alloying. -Non-metallic inclusions (oxides and nitrides) removal. Stirring of the melt and the slag caused by argon blown through the porous bottom plug results in deep desulfurization of the steel. -Temperature and chemical homogenizing. -Low losses of chromium in treatment of stainless steels. -Hydrogen removal (degassing). Benefits of Vacuum Oxygen Decarburization (VOD): -Deep carbon removal (decarburization).

During the treatment process argon is blown through the bottom porous plug providing continuous metal stirring. in which degassing (hydrogen removal) is not required. The arcs are capable to heat the steel at the rate about 5°F/min (3°C/min). Temperature and chemical homogenizing. Besides refining operations Ladle Furnace (LF) may serve as a buffer station before Continuous casting. Alloying. Non-metallic inclusions removal. CaC2.The ladle is transported to the Ladle Furnace stand where it is placed under a cover equipped with three graphite electrodes connected to a three-phase arc transformer. CaSi. Controllable reheating by electric power. to top Ladle desulfurization by injection of active agents Injection of desulfurizing agents (Ca. chemical homogenization and desulfurization of the steel by the slag. Benefits of Ladle Furnace (LF):      Deep sulfur removal (desulfurization). Alloying elements and/or slag components may be added through the addition hopper. If deep desulfurization is required active desulfurizing agents are injected into the melt through the injection lance or in form of cored wire. Fumes formed during the operation are extracted through the cover. Injection methods usually combine supply of a disperse desulfurizing agent (powder) with stirring by argon blowing. Stirring results in distribution of heat produced by the arcs. A ladle with deoxidized (killed) molten steel is transported to the injection stand where it is . which is connected to the argon supply pipe at the Ladle Furnace stand. Mg. CaF2+CaO) to a molten steel is the most effective method of sulfur removal. The graphite electrodes are submerged into the slag. Molten steel treated in Ladle Furnace is covered by a layer of desulfurizing slag. The LF stand is also equipped with an addition hopper mounted on the cover and a lance for injection of desulfurizing agents. The ladle bottom has a porous refractory plug. Ladle Furnace process is used for refining a wide variety of steels. which protects the ladle lining from overheating produced by the electric arcs.

.0002%). Injection of desulfurizing agents allows to achieve ultra-low concentrations of sulfur in steel (0. Temperature and chemical homogenizing. Non-metallic inclusions removal. Benefits of Ladle desulfurization by injection of active agents:    Deep sulfur removal (desulfurization). Steel treated in the stand is covered by a layer of desulfurizing slag having high solubility of sulfur and capable to absorb sulfides formed as a result of active agents injection. through which the injection lance may lower and immerse into the melt. Desulfurization agents are injected in argon stream. Fumes formed during the operation are extracted through the cover.placed under a cover. Stirring also provides thermal and chemical homogenization of the melt. Argon bubbles produce stirring of the molten steel and the slag promoting desulfurization. When the desulfurizing agents are injected into molten steel in form of a cored wire containing powder of desulfurizing agent stirring by argon bubbling from the porous plug mounted in the ladle bottom is used.

to top Ladle-to-mold degassing .

Ladle-to-mold degassing is a vacuum degassing method. The molten steel is poured from a tundish attached to the cover of the chamber. at which the melt stream ―opens‖ as a result of CO bubbles formation. The tundish is continuously filled with the melt poured from the ladle. to top . in which the mold is placed in a vacuum chamber. The steel stream ―boils‖ when it is falling to the mold cavity in vacuum due to the deoxidation reaction [C] + [O] = {CO}. Hydrogen dissolved in steel diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump. Intensity of the deoxidation and degassing during Ladle-to-mold pouring is indicated by the angle.

in which concentration (activity) of oxygen dissolved in molten steel is reduced to a required level.23% at 3090°F (1700°C). Oxygen liberated from the solid solution oxidizes the steel components (C. calcium (Ca) are commonly used as deoxidizers. Oxidizing refractories (lining of furnaces and ladles). In order to prevent oxidizing of steel components during solidification the oxygen content should be reduced. Dmitri Kopeliovich The main sources of Oxygen in steel are as follows:      Oxygen blowing (example: Basic Oxygen Furnace (BOF)). Atmospheric oxygen dissolving in liquid steel during pouring operation. Solubility of oxygen in molten steel is 0. aluminum (Al). Manganese (Mn). There are three principal deoxidation methods:    Deoxidation by metallic deoxidizers Deoxidation by vacuum Diffusion deoxidation. silicone (Si). alloying elements) forming gas pores (blowholes) and non-metallic inclusions entrapped within the ingot structure. Both blowholes and inclusions adversely affect the steel quality. Deoxidation by an element (D) may be presented by the reaction: n[D] + k[O] = (DnOk) The equilibrium constant KD-O of the reaction is: KD-O = aox/(aDn x aOk) or log KD-O = log aox .k*log aO .003% in solid steel. However it decreases during cooling down and then drops sharply in Solidification reaching 0.n*log aD .Deoxidation of steel Dr. Fe. Deoxidation by metallic deoxidizers This is the most popular deoxidation method. cerium (Ce). It uses elements forming strong and stable oxides. Oxidizing slags used in steel making processes(example: Electric-arc furnace. Rusted and wet scrap. Deoxidation of steel is a steel making technological operation.

318 Silicone [Si] + 2[O] = (SiO2) 30000 11.incompletely deoxidized steels containing some amount of excess oxygen. solidification of which does not cause formation of carbon monoxide (CO).018 (Al2O3) Deoxidizer Reaction A B Values of the equilibrium constant parameters are used for calculation of equilibrium concentrations of oxygen and the deoxidizer by the equation: AD/T . 1600°C) Manganese [Mn] + [O] = (MnO) 12440 5. aD=[D]. °K The table presents parameters of the deoxidation reactions for some metallic oxidizers: Equilibrium constant at 1873 °K (2912°F.BD = n*log [D] .5 4.5 13.where: aox .k*log [O] According to the degree of deoxidation Carbon steels may be subdivided into three groups:   Killed steels . aO=[O].completely deoxidized steels.activity of the deoxidizer in liquid steel.characteristic parameters determined for the particular deoxidizer D.activity of oxygen in liquid steel.activity of the oxide (DnOk) in the resulted non-metallic inclusion.BD = log aox .n*log aD . . which forms carbon monoxide during last stages of solidification. T . Ingots and castings of killed steel have homogeneous structure and no gas porosity (blowholes). The equilibrium constant of a deoxidation reaction is determined by the steel temperature: log KD-O = AD/T . BD . Activity substitutes concentration in thermodynamic equations describing chemical reactions in non-ideal solutions (activities of solutes in a diluted solution are close to their concentrations).33 1. aO . therefore: AD/T .k*log aO In the simplest case aox=1. Thermodynamic activity of a solute in a solution is a parameter related to the solute concentration.BD where: AD.518 2[Al] + 3[O] = Aluminum 62780 20. Semi-killed steels . aD .steel temperature.

Steels deoxidized in vacuum are characterized by homogeneous structure. aC and aO . Equilibrium between the two systems may be presented by the equation: . The equilibrium constant of this chemical reaction is expressed as follows: KCO = pCO/(aC x aO) where: pCO . Bubbles of carbon monoxide form in the liquid steel. Vacuum treatment is used for manufacturing large steel ingots. rails. low content of nonmetallic inclusions and low gas porosity.gaseous carbon monoxide.partially deoxidized or non-deoxidized low carbon steels evolving sufficient amount of carbon monoxide during solidification. Vacuum treatment of molten steel decreases the partial pressure of CO.activities of carbon and oxygen in liquid steel. Deoxidation in vacuum Method of deoxidation in vacuum utilizes carbon dissolved in steel as the deoxidizer according to the equation: [C] + [O] = {CO} where: [C] and [O] . Hydrogen diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump. which results in shifting equilibrium of the reaction of carbon oxidation. ball bearings and other high quality steels.carbon and oxygen dissolved in liquid steel. {CO} . Vacuum deoxidation is used mainly in Ladle refining. Rimmed steels . float up and then they are removed by the vacuum system.partial pressure of carbon monoxide in the atmosphere. Temperature dependence of KCO is insufficient. In addition to deoxidation vacuum treatment helps to remove Hydrogen dissolved in liquid steel. Diffusion deoxidation Oxygen dissolves in both steel and slag.0025*pCO at 2948°F (1620°C) According to the above expressions the oxygen activity (concentration) is proportional to the partial pressure of carbon monoxide therefore decrease of the latter will cause reduction of the oxygen activity. For approximate calculations the following equation may be used: [C]*[O] = 0. Ingots of rimmed steels are characterized by good surface quality and considerable quantity of blowholes.

about 1810°F (988°C). Dmitri Kopeliovich    Sulfur in steel Desulfurization of steel by slags Desulfurization of steel by injection of active agents Sulfur in steel Sulfur (S) may dissolve in liquid iron (Fe) at any concentration. The eutectic is segregated at the iron grain boundaries. Forging etc.). Fe-FeS eutectic weakens the bonding between the grains and causes sharp drop of the steel properties (brittleness) at the temperatures of hot deformation (Rolling.2%. When the oxygen activity in the slag is reduced oxygen ions dissolved in steel begin to diffuse from the steel into the slag. silicone. Manganese actively reacts with iron sulfides during solidification of steel transforming FeS to . However solubility of sulfur in solid iron is limited: 0. The eutectic temperature is relatively low . Desulfurization of steel Dr. In order to prevent formation of low-melting iron sulfide manganese (Mn) is added to steel to a content not less than 0. When a liquid steel cools down and solidifies the solubility of sulfur drops and it is liberated from the solution in form of iron sulfide (FeS) forming an eutectic with the surrounding iron. aluminum and other elements are used for slag deoxidation. In other words. Brittleness of steel at hot metal forming operations due to the presence of low-melting iron sulfides segregated at grain boundaries is called hot shortness. Carbon (coke). Diffusion deoxidation allows to produce steel less contaminated by non-metallic inclusions. deoxidation of slag results in deoxidation of the steel.[O] = (O) The equilibrium constant of the reaction: KFeO = a[O]/a(O) or a[O] = KFeO*a(O) Thus reduction of the oxygen activity (concentration) in steel may be achieved by decreasing the oxygen activity in the slag.013% in γ-iron at 1832°F (1000°C). oxide non-metallic inclusions do not form.002% in α-iron at room temperature and 0. and the equilibrium conditions are restored. Since deoxidizers in the difusion method are not introduced directly into the steel melt.

15-30% SiO2. The negative effect of sulfur on the steel properties becomes more significant in large ingots and castings. Transition of sulfur from steel to slag may be presented by the chemical equation: [S] + (CaO) = (CaS) + [O] The equilibrium constant KS1 of the reaction is: KS1 = a[O]*a(CaS)/a[S]*a(CaO) .MnS according to the reaction: (FeS) + [Mn] = (MnS) + Fe (square brackets [ ] . Impact toughness. corrosion resistance. FeO.about 2930°F (1610°C) therefore the steels containing manganese may be deformed in hot state (no hot shortness). They may have sharp edges. 10-25% FeO. A typical basic slag consists of 35-60% CaO + MgO. MnO. some zones of which are enriched by sulfur (macrosegregation of sulfur).signify concentration in steel. MgO. Basic slag is a slag containing mainly basic oxides: CaO. round brackets ( ) signify concentration in slag) The melting temperature of manganese sulfide is relatively high . Weldability. The properties negatively affected by sulfur:     Ductility. All these factors determine negative influence of sulfide inclusions on the mechanical properties. Unfortunately MnS inclusions are:    Brittle (less ductile than steel). 5-20% MnO. Cracks may be initiated at brittle sharp edge inclusions. Sulfide inclusions especially arranged in a chain form also make easier the cracks propagation along the grain boundaries. They are located between the steel grains. to top Desulfurization of steel by slags The most popular method of desulfurization is removal of sulfur from molten steel to the basic reducing slag.

Capability of a slag to remove sulfur from steel is characterized by the distribution coefficient of sulfur: LS = (S)/[S] Where: (S) . a(CaS). Desulfurization may be effectively conducted in the reducing slag stage of the steel making process in Electric-arc furnace. to top Desulfurization of steel by injection of active agents . Energy of the falling steel stream causes mixing the slag with the steel. a(CaO) . As appears from the above equations desulfurization is effective in deoxidized (low (O)) basic (high (CaO)) slags.Where: a[O]. Effect of desulfurization may be enhanced by additional stirring.and O2. [S] .activities of CaS and CaO in the slag.concentration of sulfur in slag.activities of S2.concentration of sulfur in steel. The same reaction in ionic form: [S] + (O2-) = (S2-) + [O] The equilibrium constant KS2 of the reaction is: KS2 = a[O]*a(S2-)/a[S]*a(O2-) Where: a(S2-). for which electromagnetic (induction) stirrers or argon bubbling are used. a(O2-) . Therefore ability of Basic Oxygen Process (BOP) to remove sulfur is low due to its highly oxidized slag. a[S] . Deep desulfurization by slags may be achieved in ladle:    The refining (desulfurizing) slag with high content of CaO and no FeO is prepared and placed in an empty ladle. At this stage the oxidizing slag is removed and then lime flux is added to form basic slag with high CaO content. during which sulfur is removed from the steel to slag phase.in the slag. The molten steel is poured into the ladle filled with the refining slag.activities of oxygen and sulfur in the liquid steel.

Ca. MgS). In the latter method stirring by argon bubbling from the porous plug mounted in the ladle bottom is used. Mg. . Injection methods usually combine supply of a disperse desulfurizing agent (powder) with stirring by argon blowing. Mg). Lime (CaO) + Mg. Ca + Al. Deep desulfurization by injection of active agents are achieved due to the following factors:     High chemical activity of the desulfurization agents (Ca. The desulfurizing agents are injected into molten steel either in form of powder transported by an argon blown to the steel through a lance or in form of a cored wire containing powder of desulfurizing agent.Injection of desulfurizing agents to a molten steel is the most effective method of sulfur removal. High contact area between the steel and slag phases. Presence of basic non-oxidized slag capable to absorb the products of the desulfurization reaction (CaS. The following materials are used as desulfurizing agents:         Slag mixtures CaO (50-90%) + CaF2 (10-20%) + A2lO3 (0-30%). Stirring providing good kinetic conditions of desulfurization. CaC2 + Mg. CaC2. CaSi.

.Chemical reactions between desulfurizing agents and sulfur dissolved in steel may be presented by the following equations: Ca + [S] = (CaS) Mg + [S] = (MgS) Injection of desulfurizing agents allows to achieve ultra-low concentrations of sulfur in steel (0.0002%).

The non-metallic phases containing more than one compound (eg. Al2O3*FeO. from which non-metallic inclusion are derived. S. desulfurization) between the elments dissolved in steel. Al2O3*SiO2. Si. Ce2S3 etc. SiO2. solidified or solid steel as a result of chemical reactions (deoxidation. Al2O3. Dmitri Kopeliovich Non-metallic inclusions are chemical compounds of metals (Fe. Al. N). Cr2O3 etc. Exogenous inclusions are derived from external sources such as furnace refractories. they are subdivided into two groups: indigenous and exogenous inclusions. MnO. MgS. silicates. MnS. C.Non-metallic inclusions in steel Dr. Indigenous inclusions are formed in liquid. different oxides.02%) they exert significant effect on the steel properties such as:         Tensile strength Deformability (ductility) Toughness Fatigue strength corrosion resistance Weldability Polishability Machinability Depending on the source. Despite of small content of non-metallic inclusions in steel (0. FeS*FeO etc. Amount of exogenous inclusions and their influence on the steel properties are insufficient. carbonitrides). oxysulfides. MnO*SiO2 etc.  Oxysulfides MnS*MnO. ladle lining.  Sulfides FeS. CaS.01-0. oxide+sulfide) are called complex non-metallic inclusions (spinels. . Cr2O3*FeO. Ca) with nonmetals (O. Types of non-metallic inclusions  Oxides FeO. mold materials etc. Mn. H. Non-metallic inclusions form separate phases. MgO*Al2O3. Al2O3*CaS.

Fe2P. which may result in their coalescence (merging of liquid inclusions) or agglomeration (merging of solid inclusions). 2. Vigorous stirring will result in . Wetting condition (low wetting angle) are favorable for the new phase nucleation. The floating inclusions are absorbed by the slag. The coalescence/agglomeration process is driven by the energetic benefit obtained from decrease of the boundary surface between the inclusion and the liquid steel. AlN. Fe3W3C etc. Growth Growth of a separate inclusion continues until the chemical equilibrium is achieved (no supersaturation).  Phosphides Fe3P. Al and O) due to dissolution of the additives (deoxidation or desulfurization reagents) or cooling down of the metal. Mn5P2 Formation of non-metallic inclusions There are three stages of inclusions formation: 1. In this case the new phase formation is determined by the wetting angle between a nucleus and the substrate inclusion. The nucleation process is determined by surface tension on the boundary inclusion-liquid steel. WC.  Carbonitrides Titanium carbonitrides. 3.  Nitrides TiN. Coalescence and agglomeration Motion of the molten steel due to thermal convection or forced stirring causes collisions of the inclusions. Nucleation At this stage nuclei of new phase are formed as a result of supersaturation of the solution (liquid or solid steel) with the solutes (eg. niobium carbonitrides etc. martensite). vanadium carbonitrides. Carbides Fe3C. BN etc. Mn3C. Growth of inclusions in solid steel is very slow process therefore a certain level of nonequilibrium supersaturation may be retained (eg. Inclusions with higher surface energy have higher chance to merge when collide. the lower supersaturation is required for formation of the new phase nuclei. The nucleation process is much easier in the presence of other phase (other inclusions) in the melt. Large inclusions float up faster than the smaller ones. The less the surface tension. The floating process may be intensified by moderate stirring. VN. Cr3C2.

Morphology of non-metallic inclusions  Globular shape of inclusions is preferable since their effect on the mechanical properties of steel is moderate. Blowing inert gas in Ladle Furnace (LF) or Vacuum ladle degassing of steel in result in obtaining cleaner steel. Excessive amount of strong deoxidizer (aluminum) results in formation of dendrite shaped oxide and sulfide inclusions (separate and aggregated). Examples of globular inclusions are manganese sulfides and oxysulfides formed during solidification in the spaces between the dendrite arms. Location of inclusions along the grain boundaries is undesirable since this type of distribution weakens the metal.La) or alkaline earth (Ca. Spherical shape of globular inclusions is a result of their formation in liquid state at low content of aluminum. Gas bubbles moving up through the molten steel also promote the inclusions floating and absorption by the slag. They considerably weaken the grain boundaries and exert adverse effect on the mechanical properties particularly in hot state (hot shortness). which considerably decrease of ductility. toughness and fatigue strength of the steel part. Dendrite shaped inclusions. iron aluminates and silicates. Platelet shaped inclusions. Polyhedral inclusions. Morphology of dendrite shaped inclusions may be improved by addition (after deep deoxidation by aluminum) of small amounts of rare earth (Ce. Such inclusions are formed as a result of eutectic transformation during solidification.  Homogeneous distribution of small inclusions is the most desirable type of distribution. In some steels microscopic carbides or nitrides homogeneously distributed in the steel are created by purpose in order to increase the steel strength. Mg) elements. Platelet shaped inclusions are most undesirable. Clusters of inclusions are also unfavorable since they may result in local drop of mechanical properties such as toughness and fatigue strength. These inclusions have melting point higher than that of steel.breaking the large inclusions into small droplets/fragments. Due to their more globular shape polyhedral inclusions exert less effect on the steel properties than dendrite shape inclusions.    Distribution of non-metallic inclusions Besides of the shape of non-metallic inclusions their distribution throughout the steel grain structure is very important factor determining mechanical properties of the steel. Steels deoxidized by aluminum contain manganese sulfides and oxysulfides in form of thin films (platelets) located along the steel grain boundaries. Sharp edges and corners of the dendrite shaped inclusions may cause local concentration of internal stress.   .

Distribution of non-metallic inclusions may change as a result of metal forming (eg. The less ductile inclusions are breaking forming chains of fragments. Mechanical properties in transverse direction are lower than those parallel to the rolling direction. Dmitri Kopeliovich Typical ingot structure consists of five zones:  Zone of small equiaxed grains The thin layer of small crysrtals forms when a melt comes to a contact with a wall of a cold metallic mold. The crystals (grains) have no favorable direction (equiaxed) and their chemical composition is close to that of the liquid steel. Ductile inclusions are deformed and elongated in the rolling direction. . Rolling). Structure of killed steel ingot Dr. Elongated inclusions and chains result anisotropy of mechanical and other properties. Heat liberated as a result of Crystallization depresses the nucleation and crystal growth.

 Shinkage cavity zone Shrinkage cavity is located in the top part of the ingot (which is later discarded) where last portion of liquid solidifies. increases due to the liberation of the latent heat.  Zone of large equiaxed grains Low temperature gradient (low heat flow) and low cooling rate of the solute-enriched liquid in the cenral zone of the ingot result in formation of equiaxed grains. When the temperature of the melt. The mold design should provide upwards direction of solidification at its last stage. which is wider in upper levels and thermal isolation of the ―hot top‖ favor to diminish the shrinkage porosity. This zone forms when the feeding of solidifying metal by the residual liquid is insufficient. carbon). Below the shrinkage cavity the zone of shrinkage porosity is located. Columnar grains continue to grow untill the heat flow decreases due to the following causes:    Large width of the solidified metal. Zone of large equiaxed grains is enriched by the impurities (sulfur. adjacent to the solidification front. Isolated pockets of liquid metal separated from the liquid pool by ―bridges‖ form their own shrinkage cavities (shrinkage pores). which sedimintate from other ingot zones. Heating the mold wall. constitutional undercooling will end and the columnar grains growth will stop. The mold shape. The air gap is a result of shrinkage caused by solidification.  Bottom cone This cone-shaped zone is a mixture of small equiaxed garins grown as a result of the contact with a bottom of a cold metallic mold and crystals and crystals fragments. Bottom cone is characterized by negative segregation of the impurities. phosphorous. Direction of the columnar grains growth is oppsite to the direction of heat flow. This process is slow due to slow heat extraction therefore the number of nuclei (seed crystals) is low and the grains size is large. Zone of columnar grains Columnar grains start to grow when a stable and directed heat flow is formed as a result of heat transfer through the zone of small equiaxed grains. Macrosegregation in steel ingots . Formation of an air gap between the ingot and the mold wall.

The moving liquid feeds the shrinking metal. Causes of macrosegregation Microsegregation is the basic cause of macrosegregation. Partition of solutes between the dendrite arms and interdendritic liquid is called Microsegregation. Segregation is caused by the rejection of the solutes from a solidified alloy into the liquid phase. The liquid is surrounded by the solid dendrites having low solute concentration (solute-poor). This rejection is a result of different solubility of impurities in liquid and solid phases at the equilibrium temperature.  Buoyancy forces Liquid phase may move as a result of a gradient of the density caused by gradients of temperature and solute concentration. Microsegregation results in formation of numerous small volumes of liquid enriched with the solute. The volume solidifies at the colder side and melts solid phase at the hotter side like in zone melting. Segregation is a separation of impurities and alloying elements in different regions of solidified alloy. Transfer of the solute-rich liquid phase or solute-poor solid phase to large distances over the solidifying mass results in enrichment (positive macrosegregation) or impoverishment (negative macrosegregation) of particular zones of the ingot/casting with the solute.  CO bubbles .Dr. The macro movements of the liquid and solid phases may be caused by the following effects:  Solidification shrinkage Shrinkage of solidifying alloy causes suction of the liquid phase through the interdendritic structure. Dmitri Kopeliovich Solidification of a liquid alloy is characterized by a phenomenon called segregation.  Zone melting effect A separate volume of the liquid phase having different temperatures at its opposite sides may ―move‖ in the direction of the higher temperature.

 Sedimentation of solid phase Solid crystals homogeneously nucleated in liquid phase and fragments of broken or melted off dendrites settle down (they are commonly heavier than liquid.CO bubbles form in solidifying steel as a result of either low content of metallic deoxidizers in rimmed steel or Ladle-to-mold degassing in vacuum. Solidified metal may be also forced by electro-magnetic field.  Bottom negative segregation . Macrosegregation zones in steel ingot Development of macrosegregation zones in a steel ingot and their locations are associated with the ingot grain structure. mechanical stirrers. Floating gas bubbles cause movement of the solidifying alloy. vibration.  External forces Metal movement may be caused by the energy of the stream poured into the mold from the ladle.

which settle down to the V-shaped solidification front. carbon.  Hot top segregation Hot top segregation zone is located in the top central ingot region below the shrinkage cavity.  A-segregation A-segregates (freckles) form in the Zone of columnar grains at the regions with structure characterized by the transition from the columnar grains to large equiaxed grains. A-segrgates present channels enriched by sulfur. nuclear pressure vessels. generator rotor shafts. Fabrication of large steel ingots Dr. ship parts and other heavy machinery parts. The largest ingot (570 metric tons) was produced in 1980 by ―Kawasaki Steel‖ (Japan). The residual liquid surrounding the large equiaxed grains is solute-rich and it forms V-segregates when solidifies. which sedimintate from other ingot zones. The central zone consists of large equiaxed grains.Bottom negative segregation is a result of low solute concentration in the crystals formed in the early stage of solidification and comprising bottom cone.  V-segregation The central zone of ingot is enriched with solute rejected by the solidification front progressing from the mold wall to its center. Metalforming technology used for final shaping of large ingots is Forging. chemical pressure vessels. Hot top segregation is formed at the final solidification stage from the residual liquid enriched by the solutes as a result of microsegregation (rejection by solidifying dendrites) followed by penetration of the liquid through the dendrite skeleton. Dmitri Kopeliovich Large steel ingots are required for manufacturing electric power plant turbine shafts. The bottom cone is a mixture of small equiaxed garins grown as a result of the contact with a bottom of a cold metallic mold and crystals and crystals fragments. phosphorus and other impurities. Solidification of a large mass of steel is characterized by significant development of micro and macro-defects of the ingot structure:    Non-metallic inclusions Macrosegregation Hydrogen in steel .

Al. aluminum.01-0. vanadium. Si. N).) o Oxides o Sulfides o Oxysulfides o Carbides o Nitrides o Carbonitrides o Phosphides Inclusions size Size of non-metallic inclusions is determined by the processes of nucleation. The non-metallic phases containing more than one compound (eg. electric power plants. S. growth and coalescence/agglomeration. Ca) with non-metals (O. sulfides etc. Non-metallic inclusions Non-metallic inclusions in steel are chemical compounds of metals (Fe. Non-metallic inclusions form separate phases. Mn. etc.02%) they exert significant effect on the steel properties such as:         Tensile strength Deformability (ductility) Toughness Fatigue strength corrosion resistance Weldability Polishability Machinability The following parameters of non-metallic inclusions influence on the properties of parts made of large steel ingots:   Chemical composition (oxides. C. Despite small content of non-metallic inclusions in steel (0. failure of which is potentially catastrophic (nuclear equipment. chemical equipment. sulfur. carbonitrides). oxide+sulfide) are called complex non-metallic inclusions (spinels. silicon. High surface energy causes the nucleation at higher supersaturation of the solutes (oxygen. H. oxysulfides. Since such parts work in equipment.) and favors coalescence and agglomeration of the inclusions. Technology of large ingots fabrication should provide minimum degree of steel structure defects.  Shape (morphology) of non-metallic inclusions . nitrogen. large scale machinery). titanium.The structure defects decrease the reliability of the part manufactured from the ingot. different oxides.

clusters. phosphorous. Ductile inclusions elongate in the direction of deformation. Clusters of inclusions are unfavorable since they may result in local drop of mechanical properties such as toughness and fatigue strength.  Physical and mechanical properties (hardness. buoyancy forces acting on the liquid metal. Platelet shaped inclusion exert adverse effect on the steel properties and therefore this morphology is undesirable. carbon). nitrides) strengthen the metal however larger hard inclusions may cause drop of the steel ductility without increase of the strength and hardness. which liquid metal and separate dendrite crystals and their fragments may be transferred. Transfer of liquid and solid phases in a solidifying ingot is the result of solidification shrinkage. Globular shape inclusions exert moderate influence on the steel properties therefore globular morphology is preferable. sedimentation of solid crystals homogeneously nucleated in liquid phase and fragments of broken or melted off dendrites. Brittle inclusions break to fragments and form chains. Ductile and brittle inclusions behave different during plastic deformation (steel Forging). chains) o Homogeneous distribution of non-metallic inclusions is most desirable. which may cause concentration of stresses during the ingot forging and decrease of ductility. o Dendrite shaped inclusions form at high concentration of aluminum. Distribution (homogeneous. Large distances. which is the main cause of macrosegregation.La) or alkaline earth (Ca. Their shape is characterized by sharp edges. Low cooling rate results in larger spaces between the dendrite arms filled with the liquid metal enriched with the solutes. Additionally solidification conditions at low cooling rate are closer to equilibrium resulting in decrease of Equilibrium Partition Coefficient and higher microsegregation. Globular inclusion form in liquid state at low concentration of aluminum. toughness and fatigue strength of the steel part fabricated from the ingot. Macrosegregation The following factors favors macrosegregation in large steel ingots:    Large absolute amount of solutes (sulfur. The effect of polyhedral inclusions on the steel properties is less than that of the dendrite shaped inclusions. Mg) elements. Partition of solutes between the dendrite arms and interdendritic liquid is called Microsegregation. Low cooling rate of the metal in the central ingot zone. o Platelet shaped inclusions form at the grain boundaries as a result of eutectic transformation during solidification. ductility. o Polyhedral inclusions are result of modification of the dendrite shaped inclusions by addition of strong deoxidizers and rare earth (Ce. Steel is being enriched with the solutes rejected by the moving solidification front therefore at the final solidification stage the residual liquid contain large solute content. melting point) Microscopic hard inclusions (carbides. .

. which sedimintate from other ingot zones.  A-segregation A-segregates (freckles) form in the Zone of columnar grains at the regions with structure characterized by the transition from the columnar grains to large equiaxed grains. The bottom cone is a mixture of small equiaxed garins grown as a result of the contact with a bottom of a cold metallic mold and crystals and crystals fragments. The central zone consists of large equiaxed grains. The residual liquid surrounding the large equiaxed grains is solute-rich and it forms V-segregates when solidifies.  Bottom negative segregation Bottom negative segregation is a result of low solute concentration in the crystals formed in the early stage of solidification and comprising bottom cone.Development of macrosegregation zones in a steel ingot and their locations are associated with the ingot grain structure. which settle down to the V-shaped solidification front.  V-segregation The central zone of ingot is enriched with solute rejected by the solidification front progressing from the mold wall to its center. carbon. phosphorus and other impurities. A-segrgates present channels enriched by sulfur.

2). tantalum increase the solubility of hydrogen in solid steel. Modification of the ingot dimensions. Decrease of the pouring temperature. nickel. Steel for large steel ingots commonly contains not more than 0. Carbon. Alloying of steel by alkaline (Ca. tungsten. Fluxes and alloying additives. Mg) or rare earth (Ce. phosphorous (dephosphorization). Using steel grades with lower carbon content. Atmospheric humidity. vanadium. Both gaseous and dissolved forms of hydrogen exert adverse effect on mechanical properties of steels: . hydrogen (degassing). titanium. If low level of A-segregation is required the ratio of the ingot height to its diameter should be as low as possible (about 1. Steel for large ingots is treated in the melting furnace and in Ladle refining stands in order to remove undesirable impurities such as sulfur (desulfurization]]). zirconium. Solubility of hydrogen in steel drops sharply during solidification resulting in formation of gaseous hydrogen form H2. Solubility of hydrogen in austenite is much higher than in ferrite. Hydrogen in steel Sources of hydrogen in liquid steel:      Damp scrap.005% of sulfur. aluminum. Factors allowing to diminish macrosegregation in large steel ingots:       Lowering contents of impurities.005 of phosphorous and up to 2 ppm of hydrogen. Hydrogen is easily dissolved in liquid steel in dissociated (atomic) state. which is favorable for depressing macrosegregation. Furnace and ladle refractories. columbium. Hot top segregation is formed at the final solidification stage from the residual liquid enriched by the solutes as a result of microsegregation (rejection by solidifying dendrites) followed by penetration of the liquid through the dendrite skeleton. In solid steel hydrogen is dissolved in form of interstitial solution. Lower pouring temperature results in increase of the cooling rate.La) elements in amount of about 2*[S]. chromium (up to 10%). Fuel (if used). Silicon. Low concentration of silicon in steel (about 0. 0.0-1.1%). chromium (10% and higher) decrease the solubility of hydrogen in solid steel. Hot top segregation Hot top segregation zone is located in the top central ingot region below the shrinkage cavity.

Hydrogen flakes

Solubility of hydrogen decrease during solidification and cooling down of steel ingot. Hydrogen atoms possessing high mobility are collected at internal voids such as non-metallic inclusions (sulfides, oxides) and their clusters, shrinkage pores, cracks caused by internal stresses. Hydrogen atoms collected at internal voids combine and form gaseous hydrogen H2, which may cause formation of cracks (flakes) when the gas pressure exceeds the steel strength. Hydrogen flakes is particularly dangerous for parts fabricated from large ingots. Vacuum ladle degassing methods allow to decrease the content of hydrogen to 2 ppm, which does not cause flaking formation.

Hydrogen embrittlement

Hydrogen in dissolved form also decreases steel properties such as ductility, Fracture Toughness and fatigue strength. Technology of large ingots fabrication The following tasks are accomplished by the technology of large ingots fabrication:
 

     

Dephosphorization (to about 0.005%) in a steel making furnace (melting furnace). Desulfurization of steel (to about 0.005%) in the melting furnace and then by a ladle refining desulfurization method (eg. Ladle desulfurization by injection of active agents, Ladle Furnace (LF)). Deoxidation of steel by metallic deoxidizers to the required concentrations of aluminum, silicon and other deoxidizing elements. Removal of non-metallic inclusions from the liquid steel in both melting furnace and Ladle refining stand. Vacuum treatment of steel in ladle by one of the degassing methods: Recirculation Degassing (RH), Ladle Degassing (VD). *Achievement of the required temperature of steel before pouring to the mold by using Ladle Furnace (LF). Final vacuum treatment of the steel in the Ladle-to-mold degassing operation. Providing non-intermittent supply of liquid steel to the pouring-to-mold operation.

The possible technological schemes of large steel ingots fabrication are presented in the figure:

Discuss the article and ask questions in our Materials Forum

Electroslag Remelting
Dr. Dmitri Kopeliovich Electroslag Remelting (ESR) is a process of remelting a consumable electrode utilizing the heat generated by an electric current passing through a molten slag between the electrode and the solidifying ingot. ESR process description

The consumable electrods are as cast or forged cylindrical parts made of an alloy to be remelt. An electroslag remelting process (ESR) starts when the lower tip of a consumable electrode is immersed into a pool of molten slag. The premelted slag possessing electrical conductivity is located on the water-cooled mold base connected to a power supply. The electric current (commonly AC) passing through the the slag keeps it at high temperature, which is about 360ºF (200ºC) higher than the melting point of the remelted metal. The electrode tip is heated by the hot slag and starts to melt forming droplets of liquid metal, which disconnect from the electrode and sink through the slag layer.

Required level ov viscosity. Controllable process. Ingots up to 200 metric tons are produced by electroslag remelting utilizing simultaneous remelting of tens of electrodes. The ingot has a good surface quality due to a thin slag film covering it. Advantages of Electroslag Remelting         Deep desulfurization. Large Forging ingots. The molten steel in form of both liquid film on the electrode tip and descending droplets contacts with the slag and get refined due to desulfurization and removal of non-metallic inclusions (sulfides and oxides). Required level of electrical conductivity. Titnanium machining turnings and foundry scrap may be recycled by ESR providing cost effective secondary titanium. No Shrinkage defects. Rolling mill rolls. Good surface quality. Applications of Electroslag Remelting        Superalloys (nickel base alloys possessing high strength. The slag composition provides the following properties:      Melting point lower than that of the remelted alloy. Creep resistance and oxidation resistance at high temperatures. Homogeneous Distribution of non-metallic inclusions Fine Grain structure. The ingots are used for manufacturing heavy parts for electric power generating units (turbine shafts. Low macrosegregation. Titanium alloys for aerospace applications. . Stainless steels. The technology of electroslag remelting (ESR) meets these demands. Fabrication of large steel ingots requires technologies providing high purity steel with low level of macrosegregation and shrinkage porosity.The slag composition is based on calcium fluoride (CaF2). The water-cooled copper mold provides relatively high gradient of temperature resulting in high solidification rate. generator rotor shafts). The droplets enters the molten steel pool. lime (CaO) and alumina (Al2O3). High solubility of sulfur. Capability to adsorb non-metallic inclusions. Tool and die steels. Refining non-metallic inclusions. Solidification front is moving upwards (unidirectional solidification) forming sound homogeneous metal structure. Titanium scrap remelting. bottom of which is progressively solidifying.

Rough rolling in either reversing or tandem roughing rolling mill. Steel strip processing Dr.Electroslag Remelting under controllable atmosphere    Electroslag Remelting under vacuum. The main limitation of the conventional ESR process is difficulty of removal of hydrogen exerting adverse effect on mechanical properties of steels. During ESR process such steels are continuously alloyed by nitrogen containing compounds. The strip temperature decreases in the rough rolling operation to about 1830ºF (1000ºC). The strips are supplied in different conditions:     Hot rolled Pickled Cold rolled Coated Hot rolling Continuously cast steel slabs are processed in a hot Rolling line:    Heating in a gas/oil fired reheating furnace to the temperature 2200-2280ºF (12001250ºC). Electroslag Remelting under increased pressure. Electroslag Remelting under vacuum provides both vacuum degassing and oxidation protection of the remelted metal. Removing oxide scale in a scale breaker. Electroslag Remelting under inert gas atmosphere. Rough rolling mills may have either two-high or four-high configuration. Inert gas protects the slag and the metal from oxidation and from pick-up of atmospheric hydrogen. Iron oxides form on the slab surface as a result of high temperature oxidation in the reheating furnace.2‖ (5 mm). Dmitri Kopeliovich Steel strips are commonly manufactured of continuously cast slabs. Scale breaker utilizes high pressure water jets directed to the slab surface. . Low content of Hydrogen in conventional ESR is obtained by control of hydrogen in the consumable electrode. The method is used for remelting nitride hardened steels (alloyed by Nitrogen). Increased pressure prevents removal of dissolved nitrogen from the liquid steel to the atmosphere. The method is simpler and cheaper than ESR under vacuum but it does not allow hydrogen removal. Coiled steel strips have the thickness (gauge) up to 0. Additionally Electroslag Remelting under atmospere may cause oxidation by Oxygen penetrating into the slag contacting the pool of liquid metal.

Drying. Other part is processed in a pickling line where the oxide scale is removed. Recoiling. . Cooling by water jets. to top Pickling of steel strip Hot rolled strip is treated in a pickling line:        Uncoiling. Part of the strips is used in as-rolled condition. At this stage the acid residuals are washed by water from the strip. Pickling in a solution of hydrochloric or sulfuric acid. Oiling. Coiling the finished strip. The acid dissolutes the oxide scale from the strip surface according to the reaction: Fe2O3 + 6HCl = 2FeCl3 + 3H2O. Passivation film is formed on the strip surface providing corrosion protection.   Finishing rolling in a tandem four-high rolling mill (5-7 stands). The temperature is reduced to max. Hot rolled strips have a thin scale of iron oxides on their surface. Rinsing and passivation of the strip. The strip dimensions (thickness. 1110ºF (600ºC). width) are strictly controlled in this operation. Edge trimming.

Batch annealing allows to achieve lower hardness and higher ductility of the steel than in alternative continuous annealing. Annealing at a temperature 1100-1300ºF (600-700ºC) in a controlled reducing atmosphere (commonly a mixture of Hydrogen and Nitrogen) preventing oxidation of the steel surface. Achievement of a required level of work hardening.to top Cold rolling of steel strip Cold rolled steel strips are used mainly in the Deep drawing process. There are two alternatives of annealing process: continuous annealing line and batch annealing furnace. The purposes of cold rolling processing are:     Further reduction of the strip thickness. evenness and surface finish. Improvement of the surface finish. Four-high rolling mill is used for tempering. In the continuous annealing line (see the picture below) steel strip passes annealing furnace at a controlled speed. Cold rolling processing includes the following stages:    Cold rolling in a tandem rolling mill. The rolling mill consists of 5-7 stands having fourhigh configuration (two large back-up rolls and two small work rolls). . Temper rolling (skin pass rolling) . In the batch process steel strip coils are stacked on top of each other in the bell type furnace.final cold rolling operation with low thickness reduction conducted in order to impart to the steel required levels of hardness. Annealing results in recrystallization of the steel Grain structure and in stress relief. Improvement of the surface flatness.

three quarter hard (150<HV<185). half hard (130<HV<160). pinch pass) produces strip surface conditions.Most of annealed low carbon steel strips are tempered since they are too soft (HV<110) in annealed condition. Hardness of pinch passed steel is about 115 HV. Bending and deep drawing operations of soft annealed steel may cause formation of kinks (cross breaks) and stretcher strains. which are the result of localized stretching of the strip at low cold deformation beyond the yield point. . Light tempering of annealed strip (non-kinking temper. Other temper conditions of steel strip are: eighth hard (105<HV<125). quarter hard (115<HV<130). which do not cause formation of cross breaks and stretcher strains.

Clean strip passes through a bath with molten zinc (Zn). Bright finish is produced by rolling between polished rolls. Oil and other contaminants are removed from the steel surface. . which are produced by rotary slitter. die).slit edges. Natural mill edges may have micro-cracks due to non-uniform work hardening. Blued surface finish is produced by controlled heating and cooling of bright finish strip resulting in formation of thin blue oxide film on the steel surface.Surface finish conditions of cold rolled steel strip:     Mirror. Superior luster mirror finish is produced by rolling between fine polished rolls. This operation commonly combines alkaline cleaning (degreasing) and mechanical cleaning by rotating cylindrical brushes. Mirror finish strips are used mainly for electroplating. Pickling. Matt surface is suitable for enameling and painting. Matt. Slit edges (shared edges). Dressed edges . Wiping excessive zinc by air knives. Rolled edges. which are result of cold rolling without any edge cutting operation. blank holder. Matt (dull) surface finish is produced by rolling between roughened rolls. from which burr has been removed. Strip edges conditions:     Natural mill edges. Bright. Degreased and rinsed strip enters a pickling bath where oxides and rust are dissolved by hydrochloric acid and removed according to the reactions: Iron oxide reaction: Fe2O3 + 6HCl = 2FeCl3 + 3H2O Rust reaction: Fe2O3*nH2O + 6HCl = 2FeCl3 + (n+3)H2O   Zinc coating (hot galvanizing). It is the common surface finish condition of cold rolled strip. which are formed by edge rolling. Hot dip galvanizing process    Uncoiling. to top Steel strip coating The most popular techniques of continuous steel strip coating are hot dip galvanizing and Electroplating. Blued. Slit edges are square with slight sharp burr. Cleaning. Matt finish strips are also used in deep drawing due to the ability of the rough surface to hold lubricant providing low friction between the strip and the drawing tools (punch.

. Decorative chromium electroplating|chromium electroplating. The positively connected anodes are arranged in parallel to the strip opposite to its surface. Recoiling. Degreased and rinsed strip enters a pickling bath where oxides and rust are dissolved by hydrochloric acid and removed according to the reactions: Iron oxide reaction: Fe2O3 + 6HCl = 2FeCl3 + 3H2O Rust reaction: Fe2O3*nH2O + 6HCl = 2FeCl3 + (n+3)H2O   Electroplating. The strip is connected to the DC power supply as a cathode (negative). Cleaning. Leveller produces smooth and flat strip surface. Pickling. Continuous electroplating process    Uncoiling. Levelling. Oil and other contaminants are removed from the steel surface. zinc electroplating). Electrolyte and anodes compositions are determined by the the deposited material and the electroplating method (Tin alloy electroplating. Clean strip passes through a series of vertical electroplating baths.   Cooling. The coated strip is cooled by air and water. Recoiling. The bath is filled with an electrolytic solution. This operation commonly combines alkaline cleaning (degreasing) and mechanical cleaning by rotating cylindrical brushes.

to top Discuss the article and ask questions in our Materials Forum .

039.4770.07 0307.70.0.:89.. .943 47..039.943 4.4.

947 57490.7089 70203 1:/8!! 70857.70.943.943 47..:89.039.3/0..943 0307.7357490. .0.039.943 4.

:89. .70.94757490..943 0307.039.3/0.943 4.73 57490.039..708970203 1:/8 !! 70857.943 47.0.943.

3:1.708970203 1:/8 $2093 :208 /:89 3480 0.3/8.9:7341570.3/.7.893 0.3/308.580307.4:8209.943 %07.42543039817424-8409029.4:8209.7...943.5174290 /039.7.4388941-494/.3/2.2.4:8 .9 #0133 :208 /:89 0.814790570.3/:897.:/0800.1:208 !70.5 3.907..5  /8.90//:73901.9 209.-7.9 3480 ...7..870.7.306:52039.9743.3/:897 08.2.

3-.209.9749.8 .3/ 5..0/.574/:.33209.307.-.0/8.4.705488-0  .70133 %0570.4:8209.98 %0574/:.9490-499424190...08808.4..84-070.3/.84:943.3/47.3/.39023.0 !:70.70.89.439.220728.0 %0.7.42-:8943.0888/0830/941:79075:7190-...4:8209...40.0790782093 %8574.070/-/884.705488-0  02.583.58. .70133 45507-:43807.507 5./:.05.3.6:/ .891:73.-05708039  43.7:80/.07907 $.7082090/.90/ ..43.38248941908.4:8209.3/84790/.4.8 .70:80/9470...9084:94390..8 %0.7090002039..300.45507-:43.209.3..088 $4790/8.3/870//3 !70./:2 !70.3/ 70.93:2.80/574...34/041.97490:80/8.82017429000..0/94 90-.02.398  7.3/0 -.45507.3/8..439.439.6:..209.455078:5.439.808.3/.98.88:.4:8209.3/ 8.7..70/94.8939424:/8  0.738..08.3.90/8..08833.3890570.9..70133574.02.3390570. 970..90/9470.:/0890144389058 .07903/.7 974:902093.9814720/.574.88.7.4/08 %0.45507--43.9749.4:8209.07 5.4:8209.082093 %70.94/0090570.0 .455079:8 5.0/ 574/:.81.25:7908  :89.88208 %000.439. .23.3//:890548:708.70.3/84793. -0.22072 .891:73..23.84/ 8.074/.0.9749.7/8./2890548:708.943574.58.07 .70348  3..3/70.890.707024.40 1:.0888.398.3/34802.307.439.90/947024.3/ 870//0/3.90 .209.439.89 1:73.

708/:01742./  .70890/ -4507.3-0800.3/8..7090309072090/47390/ 347/0794.07.0570.3/8.93:2 74:5209./.9.47397./0548:708  548:708.908.93:2209.3/0.8.08...8 .3/.90/ %0570..570.943 39..3/905..-0 330073.84 4/82093..4.07904/.9.8.87..59./  1440/-570.885430 %070.59.904784/:2.07  70850.3/ 70133  %.905.4:8209.943910774:88:5.4.90/9397.3-0 .38.39023249030.40.59.-0  800.9904/.93:2 74:5209.0 %05.070/-/884.8903970.439748..47/09470.3-070.

08806:52039 $4793.439748147570./23897.3/ 870//3 3.307.0 82093 548:708 330073.9.943 !74..8 -4507..943 .4:8209.891:73.0.

70.8 .:89. 480.039.3//:89 :89 3480 4..943.439742.9..:89.220728.549039..7/ 57490.947 .039.0. .!! 3480..3/70857.42-:8943 .439748 0.943 4.943 7.73 .3.3/0307.943./23897.943!! 0.039.0.7357490.808.0.907..

0/ %070.3.943 0.70..943 /.23..70133 .3/70.70.08.5  $4.9749.7..90/974:.7.8341...90/- 574/:.439..7.039.48 %084.3/4907:80/.9203989053..90/-0.7.408.70903../ 70889..48 08..943574.981742 89.039.7.7. .493 ..3/090209.7./2:2.../2:270.92039 %08.3/805.08808...3/897550/70.990708 .3/1.738.439.90/9 9084./2:2 5.039.54:780307..3/-4.039.9817423/:89708./2:2.90/5.3/./2:2/:89.5570 970.53.:.0/84../2:2.8 %0 70.80.0398  $2093.8../ 4.54:7 -0.039.943 0307.338.039-0370.9370.08 .7981742:30/.943 0307..48.3/84.0 80/ .70133 .943!! .0.943 4.02.3/1.0398../2:2 -0.70 !70 970.54:7/070.583472.2..5.:/08.0.3-00548:7094.98  4:804/.55.98.70./2:2-.4.8903078 .57490..:89.:89.73700.039..43/0380/.70.0890..0.7/.0880 .08.. ..2./2898 02..439.39 .

70133 39082093.

70/94../2:2/:892.3/574/:.447002039.701334507. ..43/03807 %024903209.3/0..0.893 ..0.42-:89430548:708.708:-806:039.58574.709479.80/8.0...7./2:2 ..90/94574/:./147 .3/. ./2:2.-0 5708039  #09479/89.8..547002039.3/.943 570 970.3/3.90/./2:28.0880/947024./2:2/:890548:708.98414.48..7.705488-0  093..890370..54:78.943 070.40.325:7908.5.48./2:2 !74/:.7.90/3.

9431472890/0870/574/:.  243549039.8.0/390570.08808.47/0. 1:08.0398.439748.3/0.47/0  .088..3//:89 3.3/0.70/39.-0    %./2:2209./2:2.85708039390209.0548:708.574/:.3/.70..4 47.8934507./03..70.9301742905:710/.473./2:270.3574/:./2:2/:89.0  13.0903.//0/947024.70/94../2:2209.2093549..9  .893 %0.9  548:7083.3/0..1:208.3/1:208 .-0 330073.3//:89 3.7..893.93./2:21:208.3/9030.0.943574.90/94902490389..4730 /7403.2..708:22.3 ..4:88905 .

0.439748147...9./2:2 -4507.943 ./23897.

83 4 82093.7.!74.08806:52039 $.5/070.

943 093.70133 #09479/89.

3 548:708 330073./03.

1:208  .3//:89 3./2:2/:89.9.:89.3//:89  4.:89..0.039.0.:89.0. .70.70.039..0.3/1:208 ...8 .:89.039..98414.3/84.039./2:21:208 4.943 0307.039. 3.1:208.3/.943 47.3/ 0307.42-:8943 3.943.3/.943 4.943!! 70857.439748 $4.94757490.039 8:-899:943 !74/:...943 .94757490.943!! 70857../2:2/:89 4.0./23897../2:21:208..0398.

94757490. .9 4.4730 /7403 1:/8!! 70857.943 .943 47.3/1:208  0..47/0 ..943 0307.47/0 0./2:2/:89.708970203  .039.9897088 .0.039.70.:89.

7.43/0380/.908570 970..-084.8.708970203  1:/8!! 70857..7.50307..9 1472.943418.3/.943 .574/:.3/97.9438 8009.81448 $..70..814798802039..3/805.3/90197..7.7.3/.088574/:.3/078./289.943 4507.5570 970.43.0/1742 ..0/-197.7.943-2093908.893 $003:270.943 #.943.90/94570..42-:8943.943 .0.943  %. 8:9..3.908970.90/8.5:71.91078 $003:2/:8982.088088:.9088003:2-20.0397.58003:2-.5.54:78.453../:898..890 .2.943  #0133 %8574.5.3/70947982093.3/908003:2.7.808.-0  %070.9434507.7.70.0885:7108.08808.59.80/430..893  #0947982093 %8574.-0 330073.8934507.938003:217429025:7908-/89.53.574.943 %8574.9:70418003:270.6:04:884/:28:590 384:-025:7908.0.3/8.8249038003:294.3574/:.908003:2  89.088805.0398:.08.3810770/.90/ /:73902.705708039370133 09.943574.2207247849-..39.94757490.3//:89 #09479820938348  $:5:7/4/0289.08..54:75:798003:2 %08003:282090/  /890/.2.709479/89.907.707024.92039 %8574.088.3:1.2.3-0574/:....70:80/0747.-05708039974:4:9  89.

4397481478003:2 -4507.08806:52039 $./23897..9.0.7.92039 548:708 :89 330073.5570970.943 !74.

.0.9.0.:89 ..439748 4./23897.

9079..3/.80 3..9090.039.039.73 57490.054/07.3.:.849 %08498903/70/ %089058706:70/94574/:.70574/:.::22093 0.9 -.:89.039.5488-00548:70  '.4397441-:73073480 $  #0133 89.039 0548:708.943.0599.039 4 70.70.3/.3/84793 #.039..7.80/8.970./289 4..70.70.943!! 0.58.3249038003:2 8902.943 0307.70.70.8934507.7..47409030.0.3/7:89 :898.08003:234984749078.7.808. ./2898..893 070.890/979947024.3/9084.070/ $4.943 ":03.3/9:7338 .3/84/1390209  4-.209.43/0380/.3/54/07 %08003:2 2098:80/3574/:.3-0 5708039 /0503/3439079:80/  !.3 .90/ %884.90/9...98 09.54:7 7.54:7841 507.893 .039. .70.50.0/-54:73249038003:239424:/8419057450780 ..5174290-.943!! .20 0.8.54:729:708903.0.4-..4-..7.0.7.3/ 343 574.798.:89.5 %0 84. 3480 ..708:507..58.3 %8574.943 4.7:89.0.7..3/805.0/79 4/08.943 :89.2.0888:80/94574/:.9438970.943  070..3.943 %084:7..80..50817429024903 8003:2 %0808..70/94.70 .83 $4790//798.3-00548:70940.398 .039870.::21:73.98003:2.943./070.943 4.425430398 %88..0888:80/94574/:.80.8 6:03../:894507.83:39070..408 4.3//:89  4.42-:8943 574/:.439.:89.088 $.58.893 %8574.970.0841.0397024.../08 %0574.2.70/94.3/443908.47 3/:.443.3/0307.3/2090/-00.3/9:7-30-. .3/84790/94/0391.7.039.#0947982093 42-:8943.473/38.7.0 %070.97..088084170.907.8  ./8 947024..7.089070.30/8.039.5.9431:73.943 0307.58-.:89.02.70 908.3/4-84090474730330 5.4.088.23.3/8..0.-0.0.943.508...80..0 -.0/  .039./:89 $003:21:208 ":03.039.705488-0  .02.0708/:.:89.3/.7.05:710/8003:2849.98..943 0307..92039574.3/4/0.

989708885488-0  $009.4-.439748147...3/.943  %.-0 147.48.893943498 0.2..893 4903.-0 330073.8:22.970.7410548:708..

08806:52039 .943 !74..0398 330073.3/84793 070.9 -4507./23897.893 548:708 :89 $4.439748147.4-.83 .9.0.

0.943!! 9079:80/ 14758.:89.70.70.4.943 4.039.943!! 70857..039..0.0.943  47.70.0398:-899:943 :89 94.8/43 $4..943  0307..9/0503/039:543 4.7/.../23897.039.039.0.439748 .94757490.:89..039.07 4.907.03970...039.943  0307.:89...943  0307..0.943 4.3/84...:89 .:89.039.0 ..9.943 /0503/34379:80/ 4.94757490.3/ 70857.

3 8.33.20.9094.308 700.3/ .4507..0888.907.3-014:3/32..425.:23..908.3 2.5 4984:9434184/:2/74/0 .8.708970203 1:/8 !.34190574.08808  0.2.5147100/  .5 7.3.-0147 .0884984/:2/74/08:80/940.98909338.08417.::22093 .93908./2898.90/5.9:73.//0/94/0..:23:2174293 .3:1..:230/477.:23.3/-7430700.831..893 0..439.088097.93.3/8:/089..9.:230/938.7.594984/:2/74/0 805.0-23/748808.3/209.7.209.4.2.07390/0..4817429089003/:897 93/748808.3993.7.3/8:/08 :80/-7430..3/5:25390 .07 84:-093.92039574.02.3/8:/08  84/07/748808.7.3/84/:23979047397.5 %3/:89..7.9439470.939084/:2.439039  02.3/70.5-.5708/:0 5:2539084/:2.701334507.739490820931:73..708./2898 970..5705..4.98.7./09333 %8574.98174293 .23 %8574.8.90/8900972238 700..3.7.100/8:9.:23.8 0.7093 5.7.9 %370.9508.088 '...943.3/...943 %02.4784:7. .90 84:9431742908.943 398574.

84:94394.70133.

4.93  $2093 %8574.943  0.990 1:398:5:794 7024.7.90 84:943-5./.33.074184/:289./2:2 8420743  .90/ 099099 /7390/7488947024.3/8975539093174290..8839084/:289.47301742900..3/0.70/:.33.893574..943 .93 %0/7.9438....088574/:..3/19070/94805.7:/01:73.9749.70  7024.88:5/08  .70133 %8574.3/70.0002039.547.33...03.08903.70570...80/  748882093 %8574..7:/01:73..9084:943974:00.0888:80/945.0209.0930300.90..0.0/3.4/0- ..3//7488 54:739024903209.0..088574/:.90/4/0.990 1:39.54.39025:7908../7.33.9084:943574/:..3/.08.943 %8574.39089.0.55390. 394/0870/8.90/934/09.088..4730.3/.3/5.43.943  %..79.43.09025:7908.4730 1907390708:9329:7094 805.:7 .090.-0 147.390 .3//884....90..088 25:79088:...70133834910.-.0885:71089084/:289.9..33.33 %8574.90/...88.42580/-70/:.90/934/0894..0.3.0/98:5:7.94/.088.4/08  099070133 %8574.59.9908.039093.0397.7410548:708.3/0.58903.3/574/:./947024.43.0//:89 3.08.90/934/01742905:710/ 84/:289./7.33.943.94/.908.943 %084/:289..7050714720/0390/0933370./:89-.5:71/748808..0888:80/94574/:.90/4/0830:97.73.7.088  $0993. 14720/ 822390/7488 54:73902490393.943 %8574.88.3/.553902.45507.94/08.82.8:22.:23:2947024.085:710/93174290.088574/:.9434184/:289.45507 .88.02. 5:70931742905:710/84/:289.079890/7.0  7070133 %8574..3.3/.3/2.:0817421:0/:89 -0.039 20939093209.3/.03971:.908- .3...3/197.8  :890./09333574.90.81907.8-003/054890/.4-.9090.9749..33.23574.943 %8574.3/74:8 4/04782090/94574/:.508  $009..90/934/0./ 94147290/7.4397481479370.33.0/390 ..9490-./1.08 7024.94/08  .9.33..2.390/7...9749..3/3.89390209..1197.3/.89324903209.7.0887024.0209.8-0 %88 .19079093.398:5:7..3/.39243.789..90/1742905:710/84:943- 0.3/7024.3390/7.7:/01:73..9084:943 %8/7.07 207.5700...03971:...0880/94574/:.3/197.0209.70 9.-0 330073.3/.893902490393  ..0//:89 /73900./707..3/9.0888:80/945:71.3/74:889..93-209390.9090/7.30907-0574. -209390.3/8.425090 %0 /09330/8.

943 ./23897.9.43974814793 -4507.0..

!74.9.943 .23 548:708 $4/:2/74/0 :89 330073.08806:52039 0.:23.

3/..439748 4.9./23897..0.:89!! .0.

3/...:89.471.039..943.3/0307.02.0.. .:89.080/ .039.0.408 4.039..943!! 408.943 4.70.

3..039.943 $0993.1 197.:89./09333 .3/0.943 0307..039.943 47.70.3/0.0....:89. 748882093 :890.471.943 :89.3/ 197.02. 02..080/ .9 :89 430/03910/ 4. .

0..70..708970203 1:/8 4. .408.039.:89.70.0..039.943.943!! ..943 430/03910/ 430/03910/ 4.943 0307. .3/.3/0307..02.:89.039.039.

70.408.080/ 4.3/0307.0.943.02..:89..039.3/.943!! .039.47 1. ...

080/ 47.47 1..

.70.3/0307.039.33 099070133 .0.808  4.943.943 7070133 $2093 .943..:89../289 .70133 .9 42-:8943.943 430/03910/ 0.9 .708970203 !! .9749.039..3/ 197.943 47./1. 1:208.54.3//:89 0.03971:../2898 0.

039.708970203 !! :89 1:208 0..94347..:89. .3/0307.9 :89 1:208 0.70.039.9 4.0.943.

039.039..708970203 !! 4..943 47.3/0307.:89.70. .0.943.

9434507.70897550/1742908.90/:399.2.47409030 439.784:7.4388984170.:/0897280098  5.7.3:2574/:.5..5 .5-9084.5.3:270.8.94383.5.7..80.38009 .3//0907039  .943 %094572..84-0/070.3:28..3344307..3/-4738 438:2078.0/99.2.90/-9023.54:70/47.08880/8.3/2.039.7.-994/070.3 903-0700307.7.7..3970.708970203 !! %9.90/ %08.23.9:734199.7090420.3.039870.80/-890.039.:.90/9.3.:9938 9:7338.983.3/99.80307.438:2078 4208.3:2.3:1.3.3:2 574/:.7.98 %070.83 398574.7..80 $503984.54:7  %084.084199.2.58970.84.3/4..039 0   97..:/0 070.

00.7..-0  330073.3/ .88:.432..99.1:80/8.:/0570 970.. .7.920398.43..3:284/108394.0/:708.702090/3.80/9.90/99.97.3:2854:70/39424:/8 %099./970.3.4:2-:2.2.943- 0.97470133 0.8.99.58 ..0887024.088.3574.0941472.7.084/08.90/99.943574.7.0398.43:2 5.7.893 490399.92039574.-0    %..3 %0.3 349  4397481470548:708399..3:2.3:270.5.83..39.:23:2 .-../ 5.0174290/070.3:28.7..9  $2093 !70 970..47.3:28.0/.7.3/./8 %0.974 701308 8.5570 970.84:94341/74.742:2  .53.5....3/.00.!.3//70/  0.907..907.70890/39.::2 1:73.4 %035:92.907.974701338./:2  ../:2 24-/03:2 93 7.3:28.834507.3//741:47.

943 !74.3:2 -4507..08806:52039 548:708 330073./23897.43974814799.0.9.

039.893 '# %$$&$%$ &$%# %$ $90.92039 1470.:89.8990574.07 ./23897.83 $4.:89..039/070..9 !! .08808:80/1478:71.3/902094/8:80/9470/:.3.70.9  .4397441 34801742-:73078!! 0.90/ 5720/.8 3480 4.090703..0 970..:94-4/5..808907/:7.:3/07424709.3/2574.0.439748 4.7432039.34308:71.3/5.0970.0.9203941209.550.79.943.3 0.880847408 430343 $4..109 .08907.30 2.3/84.08 8.383 %08:71.250 ..9203941209.4.039 !.-05485.25.03970.7947-08 09.8.9..90209.080/8 .92.0.0  830574/:.943 0.0/0.3.57438 43800.3/.73 57490.7.0970.390/ %8.83.-9.97470133 $2093 ./8 430343 '4.

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

92039.07  0 70.70.3-0:80/947024.0 :5.5.3-0:80/947024.23.0901706:03.9:70  3.9745.9434770.93.7432039.789..90814720/3.04:80.547.943  /89..0/:708  0 79903574.03947.07.942.1.550/3 3.088902507.943 00..3/.8.85488-094407..4397489470/:.943 ..55389.  :83.439.3/90.4:2041-..4.94337383943.308:2 2.1.078890288:.7-43.7919078.03.0 389.. 341.4190574.74507.94383/7.574.9:7.37380.7.7/8 . 4:970.398.92039814770..0.70.3/475.30 ..7/574.0..908 .3/.3..797/047/.9.398 2489..0/-:83/043..:77039 /038908.:2 743  2.83/7.0780482488 2574..4550700.92039  .9-90-70..4.70/:.0/.9:7094 S.7.07 70. 4:9 70.3..42243.4.0./090-.9.0/197.389470/:.3/0-.9072.047.8.090..425020393/7.3.907011.-.  .9384:9438 .70.0.84:3/03.90970.974/.02893 :832574.0/- 97.34/0.7-43/4/0174290.89..74:3/.3/3.0890 ..8908 $50.894.3.907 %03.7432039.439.9248507..4730.93  !:710/.850395..03.70.3/0-.94341 84/8 .-0209.4.28 :8:.7-43970..0/:708 70:.9902507.88147.3/84:3/ 4507.088.7.23..02039897:.88 .3983..088.2.0398 0053574.389470/:.7-43.943435.08.70/:./4341.0780482488..439.03.23.943 .890.370.939.939.07889028970/:.88:.439..:83247047-099070993.943970.93 .4.0890.9:708.05.:2:.333147850..3/0 0.415:71.83.9089077024..3080 .9348 94574.3/1.9017003 407390-.9370..835.7-43./847594341.3/00.090011.547..3/ 2574.3-070/:..9749.:7-.33889028 :8324/0733..8908970.807383011. :835..3-07024.0.088  .4.92039 5.8430.3/.3/73808 0  ./2:25..9 8:/08706:73970.489 9:83.9.3858 :83805.074184:94301943209..::2 0.

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

7094148 70838 7:--078.94383.0 489 84.9.0147/0.473/:897.907.547.4-.3/19:708 .4..-0. 3/:897.03.3/8:71.0398/85078047/884.93.938 .90747.884.3/.3.8.7432039.7.938 %09072.4.70347..80/ :95073809./0.209.3:1.43..84.0.3/.7/4:8-0.4.088:.94390.943574.438:2078  08341.109  03.4898.3/84.4.8090.7387024.70.93.4.0/.47547.0.03943...934507.02039  #.7..701.078 5.943 574/:.3/.70.4.93 44/. 1:739:70.0307.08909.7.4.9 %0-3/073.:80419030.4.8..:/0.0807.55.3/.-0470548.4.90.088:.70-0..7.9.7432039 3..2..3147.44:7.7-438 089078 094308 .0.//0/94.9438.3//73.3843908:71.9438  4.0.93 06:52039.9920-09003904750.930.900390.74:8 574/:.448 $4.907.43/ 90..88:.9843:2.938.3/3..70:80/ $0.39-7:8.9.9.9702.4.4254:3/ '  0288438 ' 0288438.409078.3/ ..738089457490.943/0503/843905:754804190.:738500//09072301472:..7432039.4..3 1.3//:7.425430399.8908.-9 !2039841903.4.3/.4:3907.93.39574/:.8..701.3/4:804/.057490.30/3..03/:89708.9574.4.70902.70..3/9003.9:7.0398:80/3...3/.73808 .90/ -0./ 3.93574.47147.4254:3/89.0/5.3-03.3/.9314.9381472:.4. .:7703938070870/:.3/0903/0782./08.3/80.7.398 .439.9383.38107011.8370:.6:/-3/07.30.4388903..4.-9  %095084147.08808 %0.3//0....3/5705.4.3/90 7380.439.931472:.0398.3..98..4.04507.3/209.8 1078.742.938 574.3/.4.3/.8 5:9908 44/1078 ../74.4.:708 .808.4774843.1.9389470/:..9..:/0..90/9.70.3.3088 $4.4.090 -3/078..93.6:078 03.4.98 6:/ .439.00110.93.3/ 31:03.908./0..7.8 . /74.08808 %070.55.9.03943.22.55.4747.98.370/0398 .3/ 5705.3/80.9:7.24:39417380.943 .3.:802.43.4.98 7.08  489.4257832489.943 .9438 .2.907.03088.742:2.30..90..47.489..4.4.8902.08/850780/3.90 47.03088 .70.943 8:71.93.574/:.045354:943570.70 .47850.3.0 209..:/085..93.208.3/9.3078.090 .9083.088087.93574.3.4.7.4.80 ..38809.3/45.4233..938 .0738 .943 4.3/890572.3/.0.5.944/ 3/:897.9.3.4.3520398..9383..93/:7.//9./2:2  0.425090/ 3/0783.938.307 .943 489 1:3..70:2.9.70./7.3/3.3/542078 //9.7.3.3/-:/3574/:.33..722.078 5.70 :80/3-:/38.3/57490.05705.8.34038..003.02.3/147/0.9:73.907:80/  3/:897..90.408..:94249..8 .439.109 97.34408.39.3/3.7-438 .9073.03929:70  !20398.0398:80/3.938..70:80/43.

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

03989.05705.890 5.:/0  84/.938:/017424.:/0/73 -..:/080259.90/.0.02039 $0.9306:520392:89-0.039 -...3/ ..05705.938.0 :73 20.938 47 9072480993 4240.80/.3.3078 .8/8548.938  !4/07.93.943470.938-0.43899:0398.9438 84.03943.70/9484. 240.088.33 6:52039.039 .70:80/147 .9073.70.9.9438.039.4254:3/89..8 /7.:.0.3/70833908.84.438893411305:.39' 8174284..39.90088 .890-.039 -.43..907.93478:71.4.43.4.039.0393-..908  .9432..:/0..:..07857.0894570..4.08808 $4/.80/.43.439.90717428:71.8 4.754:943..4.300.93574.3/ 70835.0 2.439.3314784.039 -..07857.43.93-3/07394.80/70:.3/0.088.3/57.907 -.0.33 411 850.4.714785039 84.439744706:52039 .90/-.4397494570.907:80/ .71.4.38283.4.0..0904070548.4390398 70/:..549039.84.90/17429080.897.308.9433.039' 0288438..907.93 1472:..94389.3/ 1478.43.7/ 94: .439.7432039.0..947.93574.0738 3.0397.9438.:73850714720/94.3/ 147.9743-0.938 .43.89083.80/.3384:9438  3890.79.90/84.0.070/52039.333447.550/ 9073.908831.347.80/.480/ 44570.938.3.9380307.02.04507.3088.3.147 05484319084.03943.3903.7 74:9302.70/94.4898780 .-4.8.3/05038.89003..3:.337./02.931472:.890/8548.7/4:8.3 4.07-01470.9.8900307.0..8  6:/.-003.425.9 .339.938 .80/.80/6:/8..4 84/84.0/:708.0.43/:.0.8903.709.8.07857.:809084.08 %0..110..07990.70/47:97.039.70.3/ 088' 0288438.7..08806:52039 !53706:708 1:83984.3/85039.4.3/06:52039.84.247317.4.3.430/970.938 55.70970831479..0 41.3/8503984.:.90/43890574794/8.38-0.4.92039889028  .3.07.7094 5:-.890.91472.8908970.90-09003 .4.4.80/./070398:71.-7.109.43.4232470545:.79.33 8503919078.0398.4898.3/..970.93.30.70.700307.7006:550/9.039 -.4.0398.94383.33 6:52039.24:394152039.93.029 43806:039  .4.943 4.80/.3/54808.9.9381742574.0.3.1.4.4 84/84.0398947024..907 -.938.890..03929:70.9.70:8:.77079.0.3/.409 9 :730307.7.908831.30/-09003574/:.931472:..9.3/.90/ 2.0.08:39.4.0.039.0/  .9438780.08:80//0907230900.80 425.0.0.03943.4.4.9.4:2041 84.907.7488 33 54/078  6:52039.8902.3470548:7094.0888:9/438 %0574.24:39841.3/0307. 858 .43974/0.4.938:83.403.89.439..0390548438  3.28.039 -.700907907245.7/4:8.090.3/.338.4.03943.08808 %8 .9434078' 0288438-09003./943.4.907 -.20..4.93 .7/4:8..:734507.1907574.9.

.088089./8475943:398 .9.4.4.938 706:73.80/ ..43/038078479072.3/%.088:... .3 4897.3:.9:8084.03943.' 0288438..039 -.8.43..700307.4/078  ##$ :43.8 0/8  7!4:943330073.43974/0.470 .. 047'.90/-.93574.9.3/#034/.7-43.

7.83/:897  !.94303.3.02039884.!7490.890.943  3.7432039. !  !741041904310774:809.3/..

943..83943 !  39073.3/7119  8-08948 70.3/#473:3  $.943..3.7430.33.548:7089409./$.. .943.89002.03898  4229900433/:897..41#0.4 03 .3:1.. #0..:50/     %##'%#$ 207.3/3.3902.9  $  7907.04190%49.473:/8 3. #   .24389470783743..47  07.3 ! 073.3/%. '039.9   .38 '4  43#  43843 47.-3472. .9    207. .147.4397.4/ 233.70 '-7.3 938 -:3..7.42203/0/!7.#8894:2.:.$..943147#080.99    $  !.25081742.     .:5.3/.7432039.8 !#..3403.943.03.4883.3/473.07320393/:897.3.43#043417.3/.0.0 3/0/  3..70.3/7.70 .803025400841.3.109#06:70203981479043897:.09. 08 #.70 74314:3/7 %050788903.039/80.42203/0/$9.7.908.884. $.8.9.943  .:7303.07 #  4347.3/-44.947.0414...9:707090 70.7432039   %42.943  3/:897.584390.3:.3/89003/:897 793/0/   74303-07#$ 0.3/..3/:5:9703 8.'039.3899:90147 .943.7/83899:90 $  $.3/.3/0.041.943 41.908 $   047$  .43.3.88-49902.109..80 $.39 33.3/&8041.7.943..34310703.3.9:735.3 #4/843 .943901307..:5.3.9099 ..90/ .7843   #0857.$9.90/ /80.7/ .

943.$.83943  $  .07-0907/0/7.887442&803 028974:7808 .4190:33 39. # $57307 #9.3  .3899:90147 .109375539.4914734507.71.3/:738  0.8( 098.3:.0944..94341-7.8.9/23897.3.1094:3.7/8 17424 8449..109.003008:3/0 2890...1094:3.943$. %0&80 .943..-. '4- 47547.$.9..943  . . 703.43/.943  ./$20933/:897:/0147254078.943413.943. 2574.3.8.883.. .3/0.-4:9  .7093%0.  !09740:2$0.7/833/:897 3/0/943 04743 0 $438  43425.:-7. .3/:!..83943 !   $.450/.3/:07  .9..43943410.744/ 23078!488-0.0 .9.0/.3/!7490.3 &$ .1..:5.3/ 254008 .:093 .90( %/8.9438  $!:- 4    3..8..3 .3/!483 507.3/3 $9473.$.  ..808.385479.3/!09740:2147.83943 !  3943   .031:990730.003      :8...0008 $   047 $  - $.3/0.   :1!:-83425.109..3!09740:23899:90 !  02897.08147439743 0.0709-02$5..$.8:708 943...943  .342.44784.330 074342.:.9.943.203:0707$..98.9$0098    9.70.3/209.398 !:-.08  4/829  '475..943 23/884.9478 793/0/      4- 47547.10930/3.9    $  .943.943 $  !7:/039!7.70 .:5.14790&80741!09740:2!74/:.109.70.7.943  4:8943% :1!:-83425.398 4- %0.83943 !   .7903   0330:0 0743428.3  !09740:2.98 4:8943 %43 425.719.3/0.3  3.9.7093.330329. !%47/.33.10 507.3/%7.9  $  '039.$07.943#06:7020398 14773/3 :113...3/:993 $   047$  207.3/8503833/:897.7191Q73/:89700079:3    :7088   #0./548:70390$0.

94  4:3 .3 3.907%0.7803..7.3:1.03943:/0  99.70.3833/:897!4:943!70.83943  $  39.3/ 0774 !/ #302.3:1.7432039.0880882039!747.02479.3.03943!740.83943  $   44507.9  09.383!4:943 !70.0 23/0/    !.3.3/#$.7409..2.3:.34439073.   70974850. .3:.9:733/:897  .9:733/:89708    7.2.943.0.33 .3/7013073 7.3. $07/.9907.9.989:/414707805480/94.4/230.9.0880882039!747.7432039./..79 .3443899:90  $243.14790..%0.3.43/.  44507.3.../$20933/:897  .8 .9.14790$0.

7-43.90 14...-0.0   O .30.8 -..0884114./070133 7 2974504.4790574.70:80/1472..3.3..0/-90.90/-90..3/ ( ../0/08:1:7.//94394/04/.94341/04/.943.8547489   '.47/3949006:.::2/0.:80/- -:--08....7-:7.9203941249038900/0.943 4 470/7030.883 094/841..889030..7-432434/0   '.9070/-4240304:8897:.57088:7041 .7..3/ 49076:.:.0 #   4 .883 ' %.738.41397/03.::2....::288902   3.::2.94341...708:9838193 06:-7:2419070.883 '..804:8..9:73../0/0..989008   '. O '.94341.79.8839403945.-847-0/-908.9430..3/4./0/0.707024.0/7403/884.883 4 #0...841.883 #  4 #0.0/3 8900.::2.:.943 '   O .::2970.::2970.943-30../0/0.943  (  ( <  070 (..0/36:/8900  /7403/11:80839490 -:--08.7089003498 7.020394190249038900.943 :--0841.92039058947024..7..::25:25   4.9..0398 4 !4/0730./0/0.:8438.7.8832094/8 ...3.3/403/884.7-432434/014723906:/ 8900 14..883  4 '.0.3/.3/7024..3/90.943-.:8438 .9:70 4..84708:983701339089001742343 209.8832094/8.7-434/.3/.808905.9:5..3:1.::2..::2 030.::2.3/90390./00.70..9430.:.0/36:/8900 < ./0 94 24//0.93.:8438.7-43/884./0:73.43903941343 209.804:8 97403   $900870130/3.   -:--08.70.70.9:5....943 O .883:909070.4207.

.394834708.943/0.4330.::2.0/0907230/-90...::2.O #0..883 #  #0.7.7.9248507.2-07.90/9490..:...94733   %08347084190.2-0794.883:39:808 .0./09249038900 6:/209.57088:70  19...:.2-07.. 1890.70220780/39490..9430.2-07-49942  3041908347088 06:550/955088:553743974:987017.

0902099478039083470 %74:90 80.7.7.:.43/83470 /43 0 90249038900148/43-.93:534304190834708 :5 0 147.3.9490. 2 743-:--08 14./0574/:..902.70.:.  9.9437..943  %0.

23  %070.06:550/9.43002039847..883....7.::2.:.//943455078  974:.2-078.70:8:.943/0.

7-:7.:84387024.7-437024.9430.9438..943  $:1:77024... %02507. /0...//0/   03019841#0.2.883  037024. /08:1:7.3//08:1:7.7.943  !70.02. /0..3/.:..3.424033  ...80.943  . /04/.43 43 209.883 #  /74037024.-0.9:70.

0  03390381089070.3..9:7094:9.943(  ( <708:9331.9430.883 ' %.O #0.0 #   /74037024.97.3/..8..43 43 209.0880 .1:73.7.8839403945.088  ! 4734/38...943  $:1:77024.3/0110..7-437024.943  #00.90/94. 706:70/902507.30.930110.7-:7.2-07 806:550/9.:.840.89..89.. #0.:84387024...0/0.0 #   3982094/.030784:7. /0.0.89.424033  O .7.907. /0548547.9438.0147 -4340343902490389008:71..2.0   03019841#0. 03!74.3.079.3..-00.80.43..883  ..94370.03943.7.943/0..440/.93 !70..0 30.883 # .844/08548547:803.//943. /0..943/0.943  03.:.02.:.3.. .7.943  !48547:87024.8839403945. /08:1:7.9.99070147090970..7-:7.0  /..883  ./00. %02507.90/209.9:70.3.

390%...74388:550//:73..3.92039 %0708.::2 970.3/.//3.2-07...//943455079.::2.07 %0455078 :80/147..2-07 %0..0/394.4390...5474:8 7017.4.30./0806:550/9.8832094/90 .430020398..9475:24:390/390./0924903890085./0-49942 %74:905:.::24..

 /0...:8438 4/08..3/7024.424033  .708:983/005/08:1:7.8548808838:1:784:-9.93.:80889773  .0897734190209.41397/03..943(  ( <89.//943.70:80/398574.3/397/08 7024.::2.943  !70.43 43 209.7-:7.943  0058:1:77024. /0.804:8397403   03019841.3/...3/ . /04/.8..3/ -:--08.943  ..30.883  /74037024..80.02./00.7-437024.883  037024.7933908900:3/07.. /08:1:7.478.743-43974:90-499425474:85:  39038.3903810/-.841.3/908.088  743.883 ' %...9:70.425430398  %070.0884114.43/9438.3..:8438.. %02507..94341908900  08:1:738.4790574.

00.425090//04/078.0  1907.::2 030.088..7-:7.99070147090970.. /08:1:7.-00..90/94.390/0.::2 030.943(  ( <7.438:20/2..943  .3-9070.920394189.7-:7.//0/9490249038900 8:71..4894/0..2...3/908.93472.3.43.883 . 706:70/902507.9438.943  44880841..57088:70403 8.7-437024.7-:7090890092347..0403 %03.943 '  2094/8:80/1472.O '.930110. /0.9:7094:9.3.308889008  ' 574.0 147-4340343902490389008:71.743-43974:905474:8-499425: 708:983/005/08:1:7..840.94341908900   03019841'..088.0.03943.::2 030..3:1.3-4/. ..943 '   3982094/.308889008 /74037024.943416:/8900..943 '   005.883 ' %. /0.0.3...9079..7-:7.0  '.8902.90/209..94370.43899:0394189.:80/-.70..308889008  /.7-:7.742:23970.94341.883  $:1:77024.//0/94908900 347/07947024.::2/1107817429..943 89.742:248808  /.9:73$9..2-07806:550/9.0 $97734190209.7-:7.943 4/..425430398:3/07../00.079.907...440/.30.//943.9.08:1:738....030784:7.8.742:2  .

93 43 209..3/. !70./0:73.80...90/9490. %02507.3. 5474:87017.3/8..70097.3/.90/ 70130/ 3.9475: ./02.0/../0:73.4.80.3/397/08 7024.089..94341/08:1:73.3/  %089.38147207 %0.089./0:73.0   490389003.8.3.//9434550724:390/4390..9700 5.7./0.43 #00..0706:550/ 997007.0/:3/07.07   49038900970.424033   94945 .-0 970.3/070985.90/974:90 .8.3854790/9490..0    %0..7438:55550.0147 30../0897.0398 :20814720//:73904507./0:73.4.59000.943.8406:550/9../0-49942.4330.4.4....9:70.07.02.0.08.3.0741/08:1:738.:8438 4/08..90/3./0:73.590 .4330.974/08. %07.90/94..97.990.070/-.

/03317424.5.9890.7.8 %0.90.070.-4:9S.0/-9000.-0940.708:-2070/394908.00. .8.70.97.974/08.93 574/:...7.9908900.9907.57490.

23 S.

9574/:.23   :7390970..943.94341908900-908.8 .088.0/-90.89773 $9773708:983/897-:943410.7438-43974:90-499425474:85:574.7./3 .4393:4:8209.3//08:1:7. 42403.02.92039574.3/.   430020398.

424033 43 209.943.42-308:5541./0..  30.90/39089.0..039830. /08:1:7.84574.9.4.883 /7403 7024.90/3.94389.0574.. .94341.3/22078039490209  $900970.0/:3/07.070/-.9.//94345507   1/005/08:1:7.807.//0/974:90.0398 .97.478.$ .7438970.0741/08:1:738.0.8.0473147241./0:73.3. ../089072.0  2.5.   ..9.:84387024..039 54/07 9 89773-.407.893   03019841.02094/418:1:77024.0..  ./0.-:110789./0/08:1:7.07 974:.93-00.708:941.9434190209   0390/08:1:73.94341/08:1:73.943 $9773.0398.../0:73..3/07098 5.943.-0700.-847-8:1/0814720/.943  43974.02..3..0398 30.. 42403.02.02. 94..0/08:1:73.0398.0   O O O O O 0058:1:77024..3/.0398.9432094/8:8:.439..4.743-43   .9030.90/3942490389003147241.9.089773419024903 8900.7030.943  08:1:7.9438706:70/./09/04/0/ 0/ 249038900897..-0. 8349706:70/   94945 ...2490389008902489 0110.7030.384:-941 8:1:7.3/908./0:73.470/70   08/08701334507.7030../850780/08:1:73.-094.3/.33 .90/39490209974: 9030.9438.3/.943-014704393:4:8 .3854790/949030.8..5742493/08:1:7..0888:80/14770133.470/70.3/8..5407 43 %02507.2 743-:--08574/:.4254303982.7094189008 3.9:70.943-30...943.3.

 /08:1:7.02.943..9:70.0397.4.3/..  .9438418:1:738900    03019841.94341.43.943  %02507.94341/08:1:73./0-499428:80/   :20814720//:73904507.90/974:90./0/08:1:7..4894.:84387024.03989773-.0:97.743-:--31742905474:85:24:390/390 .424033 43 209. 4..3.0398.9.0398 O O O 0058:1:77024.54/0741/08:1:73...70097.0.07   30.943-30.0..

/0 94 24//0.   94945 .883 .

::2/:09490/04/.889030.::2..90/-90 ..943(  ( <   /7403/884.::2/0.2-07  %09:3/88.2 -48 03981.074190...708:941 -:--081472..93.8..3949024/.99.4..90/-90 ..0/9490.943...4393:4:810/99020954:70/174290.9.../0   %089008970.30 ....8838.2-07   %0249038900854:70/1742.902098970..:.3//0.883/:73.::25:25   3903894190/04/../0 94 24//0.. .943    .0/3..9024/85.2 45038 .8832094/ 3.3/90.0/38900/11:80839490 -:--08..9:3/8./0 94 24/54:7383/.943 70.

084.97.94341..:73.7.90/.:73.7.974/08.9  .9   %43/84100.42243:80/38900 2.97.3/.3/2090/ -0..7.89002.:73.97..7.../03900.70....../.97.:73.30..30.08   8907 .7.33:594 418.. 9  O O O O $97:.30.0897.7.0 #017.97. 03:73.97...3   %02.3/58.59000.5 -4:94190.0 507.:73.-994970.9410.31:73.08/70.580.97.7.:73.9:7041.:770392.3/90209.88973-09003901:73.:73.708.7.97.0790.:73.974/08.30.:73..439.-0:80/30.30..000..:73.9:7041.97.9073.70.0  8.97..7.7:/08900390 47/82.08    .3.5.574.0 3.9.02.7.97..0  .0 $97:.7..:73.5.89008..0   7 2974504.088083.7.7.7.-.  0..94100..9473341.7.97.0....:73.800.8.97..041900.0 02.93   %700 5.39.97.

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

8.43..3.43.3.8041 03..//943.4/3  7434/0.088.7949.088882..00.439039390249038900.:7-7...3/43470 0 8:80//:73904/3 5074/  .7-43 5485474:8 8.804:84032.8   0 0(  (  03/884.30804/0  %0574. .:8083.70.93.7-43 5485474:8 8.098< 3 ..0/3902094/08.4/38.-0-4339490209147..0.098   38.425480/4120 ..3/2... /389.3080  (  ( <  $(  < $    3( .943 86:.3/2..0   . 03:73.098( 83184:94338900 74:3/-7.70-7.8. .0  99889.47/3949070.

 < 3   !( .

804:8574/:.93:5974:90209708:93 70133419089001742343 209.70..3//74037024.   .9070/-905489 .7-432434/05. < !    .  -:--0814.-847-0/-908.3/ .:8438.42-:89437.924850708.7.94 <.79.4190 .3.707024...:89388902  /3549039.92485070   <  < <  %014720/4/08.0/-900..-:738390.98 .

0  08. .8701334190890017428:1:7.-8475943414/08 14720/. 708:941/04/.8.3..94341-.3  #0/:.//0/.  <  <   %04/38.037.094.0147 1472.43/9438   %01:3..8.3/49074/0814720//:73985074/8 7024.943 3   .99889.425480/2.34120 .0/95485474:8.389.94341988. .0/1742901:73.3/.70/:.1:/07 8.549 /0 8.88.8.

73 093 $.943 /.8:702039 0 8.8.943  $(  .9433.3.947332.3.441743 .253.   430020398 7  4 ' 09.425.1472.70/945743 6:.3903..0 ..47.253.8.5.399084125:790805485474:8 8:1:7.94341 ! 3 $   $.3 .0/-209.30.3..7-43 :8:.3.02.943   32.439..70/:.-847-0/-908.7.:8438..7050714720/4:98/041901:73.1907/04/.553908900 #017.3/.:594  $900..:73.943  7 2974504.3.3.0  $9002..943 .70.0403/884.33:59441.%00.884190209 /38.1472.70..0949070..3/8:1/0343 209.088.97.9:7020.//0/..93 .3/902507.943 04/3 3  43 %..0.80890574...38407 .7.439.3 3974/:.-0147/08:1:7.0880841 3  /04/.0/390209/:734/35074/87024.943 /08:1:7. /04/0783 $   3(  ( 3   $(  ( $    (  (     . .$   (  /0..38.0 O O O O O O O O O O O O $.  $9008.47/.94341.3/13..81.3/ 8.  .43  .43./070133   94945 507.8.

...088890248954071:. .4031:73.8.8.403.8.8..4.9:70  %5.07907.70 O O O . 03!74.0    -..0204190.0 -./0209.43.8.32094/8..8.43 .97.90.84397:33438  ..0 .89008030/97017.8.9.5.02094/4189002.770133  .370/:.3:1.389002.08808 3..088  !  0.43/..3/5485474:8  %02.3/0110. 03!74.43.24:39841. 03!74.-094749.7.390.9:73   %08.7-43 8.94733  %01:73.088  !  %0.8.08.$9008574/:.. 03:73.0/17425743-574.1:73.-.079.07907  857080390/3905..403../070133 .:7 80.-4:99847439.

81:0  %089002.7.088390403.0147-4340339490 209  %0-.253.//943.3/5485474:8 807.5  !4:736:/5743394901:73.07907.2.55390890094.440/403.-847-0/-908....088.8..9:594 9.907..0 .943830.25390209.7147.0.8.9 30..  %0403.-4:9 23   94945 0.3/54:73 908900.1:73..07907.0  %0.737./0  0 8.403.. 03806:550/990.70.4.3/574/:.3.731:08  03-43  $.041.43.714790574.5.8.3574.9:7020.3/908.43  2.8:702039 %.3080.07907:80834. .3/902507.4:941901:73.43..088  %0147234/08.97.7389008.30.3/1:08 8.088.943.43889841 O O O O O O O .3  %074325:79084/0 0.907.7-43 8.7.1:0 %0574325:7908 .3/8:1:7..3.8.%8749.43.0  .

793905407 2093  /389.9 574/:..0/  O O 0 8.97.7.87024.0..389.7.97.59000. %000.//0/.553 .079..3.974/08147574/:.38.7.397.:77039 98.-847-0/394908.3/.  %01:3.5  %089002.3080 %04/08.8701334190890017428:1:7.5.3/.0 01:08 20..43889841 O O O ..70/:.9:70  89000.8 897343 9490..3/89.94341988.94341-.70. 9003/419089.70. 5743 2089430 40739000.7.8 ..01471472..9399490706:70/902507.:8084/35485474:8 8.97. .3/ 2. . .7.5209.0900.-094 209:594 4189008.0:9089009073.1:73.99889.1:73.7.3574.3/0.7..0025489700.0/-90.0908.97.90 .3 #0/:. 708:941/04/.1:73.974/08.473410307 00.0 99889.7.-8475943414/08 14720/.3.943  O %.8.08839000.8.43.70.738.

/070133 ..:808574.9:70. .7.80  30.943970..::2970.9430.25041..9248507../0209...0.4507.883 # .3/49078  .70.920393.943974:90.883 902507....92039-982094/  ./0.9.8 5:73.98900904507.7-434/07024.743830....8807 .43  94945 .::2..8902507.:7 80.-0..00/3.7.::2..56:.::2.0  %0..94341.O 332.8939905:75480841/08:1:7.3903.943 390.81448 O O O O &3290/8.43/:.02.93 .3992.94341906:./0701332094/8#0.43974 005/08:1:7..344..943 /0..-0209 .0880507298./0574794 ./0701338548989002.  .43/.57088:70 .08419000.8. .3/897739089009409079908.02.7..::2 2.80.70./08/0:80/  '.:808900./0209..7.:.:..390.9438 50714720/390.//943411:08 .3/49078 39490.90/  743-:--08 24.3/..9..43889841.399414/03. 42403.::2..9:70.943416:.7/8 . .00.943 /04/.770/4:9.943 !70..1:73./..4.39.93/08:1:7.943. 03:73.0/7403 /11:8339490 5.3:5.0880 //943841 1:08390.770133  .:7850714720/-.943708:98370/:.3..9439390249038900 (  ( < %870./0701332.:8438  %0-:--0841.-847-38:1:7  390574/:.::2/0.0    .97.3/89773  $:1:770133 /08:1:7.3.08809949:-08 834708 220780/3908900  343041909:-08.

9:70   %5..-.3/58.  %0.0.08808 507.0 3.7:/08900 39047/82.4031:73..-.7 2974504.32094/ -4:94190..0.07907 890248954071:.9/0598 .. %0-. 03:73..94733  3 41901:73... 03:73.0  %08.089002.088030/97017.3/0110.8..5.8.31:73.8.8...0   8.0 . 03 43.90/24903209.02041...8.8...088 .7.0   857080390/3905..8. 03$9002..8.9:70 #017.4:20810/990970..08    O O O O :73. 03:73. 03:73.94733 02..3 .8.43.9.  .3/8900 8..94341403-4339490209:3/07.249035743.0897:.943 $97:../0390.0793948900/:0944/3.574.079. 03:73.8.8. 03!74.9:7041..8.89002..

.5..249478  %8749.08  9   %0.03-00.-49942 .0880..7147..0880 8.8.3/:5507.907.43..5.80.97. 03:73.4031:73.0880/:73403-43  %0.0/94.440/403147-43 40339490209974: 3408  0314.08  19.3/7./0889.08     %095.943 993 830..088..4224370.2.430 %0...-094749.3//.84397:33438/7.8 8.2090741901:73..94-090039009..737.8:5547937306:550/997:33438  %08:55479373574..079078.90.25390209.907..-05489434190.43.8..0806:550/990.-4:9  19    2 %07.7988507.07907   %0945-43-.4388984197005..3/54:7390 89004:94190.94190.-4:99847439.99.

23 9   2.

8 5745.38 570...940.949033 .808  5740.7  8.3/57490.2.8.440/-0907/74.93708/:....574.43/943841902507.9:70.781.947-7...3/9:738394.419024903209....9472.9473341.4031:73...7-4330947-3/3907017.3/ 4/3.48945744390807.0941909:-0   94945 #017.8.0 .8-97403-43974:90.43903941.8.30   #017.8908939043041.0806:550/9  9:070814730.90/8..98   94945 02.939033901742..99.94341 403 4740392054/07 %09:0708.702.99904/38. 8.088083.3/-:73920 .308.0 0. $07..010419033 O O O 439744190.0  O #05.3/58.907.814733-.3.9473341-.0 %07017.30 209.8.439..   %0144320.3.01041403.9:7.790/.8.02..04/34/00 3908.0847380.0/4308419033-:3337017..2.40/. 23 9 %040357088:708  58   !.070.85..8:708.9477.0 8.7088. 03:73.98   %0-49942-43-..8.8..-4:9 0.8  !0714723 8.7-43. 03:73./04109077083-43/0/2.30 4748:550/94904:907.807.92485070 %0330.0  //94341 94908.8   !745072.30890  ..3089047 9....30/332.4031:73..39.03930993-90 8.08. %0-43/32.4031:73.907. 7083 9.70.7-43/0/29:708412.

43  2..9070.9 30.8 8...088.90/574..3/9825:79084/00.:7-7.30.-057080390/. 3.3080.3/5485474:8 807.8   . .304:84390-4:3/.943419024903209.3/908.8..  8.0.%0-.425.088   /.0:80834.088574...70-7.8.81:0 743. .89.:77382:9. 209.8 209.098< 3 .3/4.4031:73.00/3380.7-43 8.07.098   38.//943.1:0 %0574325:7908 .714790574.708-09003/11070395.808 .81448 86:..08 .94382.3.4.098( 83184:94338900 74:3/-7..

 < (  0( .

 < 0   $(  < $    3( .

 < 3   !( .

 < !    ( .

 < <   < .

   .:893 88902  /3549039.7097.0/-900.98 . < <  4894/08.3810770/9490.4190.3/ .94  <.924850708.-847-0/-908.42-:89437.3/7024..9070/-905489 .70.804:8574/:.92485070.7..

8 .7.731:08  $9..418:1:717422490389009490-.4303990/54894341901:73.8.088.0.4:50 ..8. 03:73.72094/41 /08:1:7.7389008...38..-0.3 907014702.253 %02507.0  .2508 147.94387024.0888.7009  !4:732490357431742-.0/3908.14720/390..702.9:7020. 03:73. 03!74.3.943841.0790 8.70/:.9434190-438.8.0  . 40.:0 41/897-:943.-4:9 .2:2.2..-9147/08:1:7.02..3/9.943 %02489545:.8:7020398 -/8548.039418:1:7390574.5   4190949.0 O O O O O .38.88..084/3 34970/:.-090724.94341.439.0397.   94945 507.  <  <   .8293..8.33.793403-43 :7.891:73.4011...43./0974:90:5507.-4:9 23  $.

020394190249038900.7-:7...0.3/90.::2..-4:9  23  .93..92039058947024..:8438.41397/03.5 94 9./070133 7 2974504.9430.5.943 '   O .943. O '.889030..9.7-43/884.804:8 97403   .943-30.....:...94341.808905.943 :--0841..0/36:/8900 < ..8..77 4.3/.3/403/884.39490.3/ ( .943  (  ( <  070 (.//94394/04/.943455489094909./0  O 0 8.0   O ..07 41908./0.883 './0 $50.94341/04/.3/574/:.9:594 9.47/3949006:.:..79.9:5./0:73.::2.8839403945.0/7403/884.::288902   3..::2 030.84708:983701339089001742343 209./0 94 24//0.4207.70..::2.:.7-434/.3.089:730/:58/0 /43390/70.0/3 8900.0 9.841.0884114.5 41.883 4 #0...-847-0/-908.0/-90.::25:25   4.3/7024.3/...394908.883:909070.57088:7041 .039 503097...94341.804:8.90/-90.7./00.9430..30.0398 4 !4/0730.943.::2970.943 4 470/7030.70..943-..90 14..7-432434/014723906:/ 8900 14. 03:73.3/90390..55340  O %0.707024..8..0/36:/8900  /7403/11:80839490 -:--08..3 54:7390708/:.9478 570.883 ' %..7.::2970..0 #   4 .7-43..   -:--08.883  4 './0/0../0/08:1:7./090.943 O .:80/- -:--08.:8438 .883 094/841.549 %01:73.7-432434/0   '.553 54:7390890094./0/0.4790574...9:5../0/0.08 5:8 8..943 .8.9203941249038900/0.%.0.708:9838193 06:-7:2419070.3.883 #  4 #0..

.70:80/1472.2-07.0.$900870130/3.943/0..90/9490.8 -..989008   '.:8438.3..9:73./0/0..4330.::2..94733   %08347084190.-0.43903941343 209.::2.2-07.8832094/8 O #0. 1890..70.7.9070/-4240304:8897:...738.3/ 49076:.394834708.8547489   '..883 #  #0.2-07-49942  3041908347088 06:550/955088:553743974:987017.7089003498 7.2-0794.:.57088:70  19.3:1.0/0907230/-90./09249038900 6:/209...8832094/8.7..7..9248507.::2.883:39:808 .70220780/39490.9:70 4.:..::2/0..3/4.::2....9430.

0902099478039083470 %74:90 80.43/83470 /43 0 90249038900148/43-.7.3..9490.9437.:.. 2 743-:--08 14.70.7.943  %0.93:534304190834708 :5 0 147.902.:./0574/:.  9.

06:550/9.7.43002039847.::2...2-078.70:8:.//943455078  974:.883.:.943/0...23  %070.

7..883 #  .-0.9430.3//08:1:7.2.:.//0/   03019841#0.9438.

3.943  .-00.9:70.0   03019841#0..97..0880 .7.9430.7-437024.9:7094:9.:.7.9438.943  $:1:77024.89.94370.0/0. 706:70/902507.8839403945.7-:7..3.2-07 806:550/9.0 #   /74037024.840..2. 03!74.//943.0 #   3982094/..8839403945.943(  ( <708:9331.0  03390381089070.7-:7.:84387024..0.079.....943  !70.883 # ..89.7-:7...:.3/0110.907. %02507.8.943/0.7-437024.0 30. /04/.. /0.:.424033  O #0. /08:1:7.088  ! 4734/38. /0.440/.1:73.. /74037024..3.0  /.844/08548547:803.43.7.883  037024...7. #0. .43 43 209.02. /0.930110..03943.943  .80.943  03...90/94.99070147090970.883  .3.90/209. /0.89.943/0..9.0147 -4340343902490389008:71.030784:7.3/..3.

883  390%.3.9475:24:390/390..::2 970..80.430020398.3..4390.2-07 %0.943  #00../00..424033  O ../0806:550/9.93 !70.0/394. %02507.92039 %0708..5474:8 7017..3/..9:70. /0548547.883 ' %.//943455079.943  $:1:77024.::24.//3.07 %0455078 :80/147.4.30.. /08:1:7..:84387024..30..43 43 209.74388:550//:73.2-07./0924903890085.::2. !48547:87024../0-49942 %74:905:.02..3/.8832094/90 ..

3/ -:--08.:8438.478.8548808838:1:784:-9..43/9438.0897734190209.088  743.4790574.804:8397403   03019841.94341908900  08:1:738.::2.41397/03.3/ .841.7933908900:3/07.30.943(  ( <89.708:983/005/08:1:7.0884114.425430398  %070.3903810/-...883  ..743-43974:90-499425474:85:  39038..3/7024.8.70:80/398574.3/908.93...883 ' %.:80889773  ./00.//943.

2-07806:550/9..308889008  ' 574.7-:7.3/397/08 7024.424033  O '.9:7094:9.::2 030.0.7-437024.57088:70403 8. /08:1:7.3.943  0058:1:77024.0 147-4340343902490389008:71...//0/9490249038900 .3.94370.70.425430398:3/07.99070147090970..9:73$9. /0..907.8.088.943  !70.-00..03943.9079.. %02507.7-:7..079.3-9070.425090//04/078.8902..9:70.883 ' %.4894/0.943416:/8900.::2 030.308889008  /.08:1:738. /04/.//0/94908900 347/07947024.7-:7.43899:0394189..94341. /74037024..943 '   3982094/.390/0.440/...80.943 89.3..3. /0.. .9438.7-:7.9.3:1.7-:7090890092347.02..0  '..:8438 4/08./00...883 .0.43 43 209.943 '  2094/8:80/1472.0403 %03.90/209.::2/1107817429.030784:7..93472.00.840..0  1907.438:20/2.742:248808  /.30.930110.3-4/.883  037024.943(  ( <7..2..088.943 4/.90/94..//943..742:2  .3/. 706:70/902507..943  ..43.

943 '   005./0:73./02.0/.90/ 70130/ 3.80.0   490389003.0 $97734190209.7-:7.-0 970.:80/-.9:70..424033   94945 ..7-437024..920394189....883  $:1:77024. /0./0......943  44880841.3/397/08 7024.743-43974:905474:8-499425: 708:983/005/08:1:7..:8438 4/08.308889008 /74037024.94341908900   03019841'.3..7-:7.0.43 #00.93 43 209.742:23970.3/908... /0./0:73.0    .::2 030...02.8:71.3/.943  !70.. /08:1:7. %02507.

.07   49038900970.7.90/974:90 ../0:73.90.4330..070/-.9907.59000..9700 5./03317424.8.990.97.//9434550724:390/4390./0:73..3/8. 5474:87017..57490. %07.089.070.0741/08:1:738..4..9890./0897.93 574/:.3/.4.90/3..9908900.4.94341/08:1:73.3/070985.08.0/:3/07.70.3. .-0940.5.97.3/  %089.974/08.-4:9S.8 %0.%0.0147 30.7438:55550.8.70097.90/9490.0706:550/ 997007.90/94./0:73.590 00.7.708:-2070/394908.0/-9000.4..089.07./0-49942..3854790/9490.8406:550/9.80.7.8.974/08.3.38147207 %0.4330.9475: .943.0398 :20814720//:73904507.

23 S.

8 .4393:4:8209.89773 $9773708:983/897-:943410.9574/:.3/. 42403.0/-90./3 .943.94341908900-908.7438-43974:90-499425474:85:574.   430020398.02.088..7.92039574.3//08:1:7.23   :7390970.

0398.3/07098 .-:110789..94341/08:1:73..0  2.  30.7094189008 3.   .93-00..94341.94389..9438706:70/..424033 43 209.883 /7403 7024.//0/974:90.943.9. /08:1:7..943  43974..0473147241./0/08:1:7./0.02.0574.039 54/07 9 89773-.0.3854790/949030.97..:84387024.0/08:1:73..4254303982. 94.807.9:70.470/70   08/08701334507.9.0398 .-0. 8349706:70/   94945 .$ .478.90/39490209974: 9030.-0700.9.9438.8.0888:80/14770133./09/04/0/ 0/ 249038900897.943-30./0:73.7030../0.3.0398 30..3.0   O O O O O 0058:1:77024.893   03019841.42-308:5541.02094/418:1:77024. .743-43   .5407 43 %02507.0./850780/08:1:73./0:73.943-014704393:4:8 . ...2490389008902489 0110.//94345507   1/005/08:1:7.3/.9432094/8:8:.  .../0:73.

9.439.33 54/0741/08:1:73...2 743-:--08574/:.5742493/08:1:7.070/-..8.9030.470/70...384:-941 8:1:7.708:941.7438970.9:70.90/974:90..  .0398.3/.943..743-:--31742905474:85:24:390/390 .5.0:97.02.:84387024.02.7030.-094..0398 O O O 0058:1:77024.9434190209   0390/08:1:73..0398.0/:3/07.0398.9438418:1:738900    03019841.943.3/.4.4..3.3/908.03989773-.424033 43 209.089773419024903 8900.943..9...3/22078039490209  $900970.94341/08:1:73.407. 4./0-499428:80/   :20814720//:73904507.943 $9773.0.943-30.0741/08:1:738. /08:1:7.0.4.94341.3/..90/3.90/39089. 42403./0/08:1:7.-847-8:1/0814720/..943  08:1:7./089072.07 974:.84574.7030..43.90/3942490389003147241..07   30.943  %02507.02.70097.0397.5.3.3/8.039830.0.4894.

/0 94 24//0.   94945 .883 .

99.90/-90 .::2./0   %089008970..0/9490.8832094/ 3..3949024/.943(  ( <   /7403/884.9.883/:73.943 70.902098970.2 45038 ..8..::25:25   3903894190/04/....93.2 -48 03981.90/-90 ...:.708:941 -:--081472.0/38900/11:80839490 -:--08.9024/85...3/90..943   94945 .../0 94 24/54:7383/.2-07   %0249038900854:70/1742.. .3//0.074190.4393:4:810/99020954:70/174290.889030.4.2-07  %09:3/88...::2/0.::2/:09490/04/.9:3/8.943.30 ..8838./0 94 24//0.0/3...

753$4/1.1:73.70.0397.384:7.7/04/.943-.336:/8900/:7354:734507..943-209.70.943  04/.943 /37017..9   347/0794570..9  41403/884.0/94..:8438.425430398  0 .403/884.0/   04/.42243:80/.7.:84380397.3. 03:73.443/43.94370.-04/08  .2500...:23:2  .94390403.5.8 /04/078  04/./08  #:890/.3/89.97.3/903/74588.../04/078 04/.3/343 209.943 .43903984:/ -070/:. .9  S  S 40.0841 0338900.70...7.9.99089006:.5  $4:-94140332490389008 .390.0   %070.943418900 7 2974504.07:2 0 .89002.344.9432094/ 9:80800203981472389743..3/.110..943-209.39 419070.8:80/389002.250.  %02.0394/3418900.4507.3/098.::2 11:843/04/.079/0.943  3(  ( 3    %006:-7:2.:2 .81448 O O O O O 03-43 0..9438   .9432094/8 O O O 04/.4389..43 0020398 14723.854708 -4408 .3 384/8900   03-07..-057080390/-9070./04/.3002039  2.90/17429084/84:9434/08908900..3574.550/9390349 897:.04/.0    /38.430 $ ..08808 0.0780.3.425430398/:7384/1./.8.9434189008.709700573.4.943 3.0 9248507.808/:73 .9:70 49-4408./04/078 %88902489545:.43.3/3.943-.0/3249038900870/:...94708 33411:73.. .706:70/0.08.3080 3 8.

3.  4. .   47 4 4.  .4 3 4.

.9438/08.943 .84:903.9.98:-899:908.70.84:9438.3.9.4 ..943390724/3.7-3 ..941904/0 3  390708:90/343 209.9438   %006:-7:2.0397.3941...7.48094 907..0397.02.94190/04/0736:/8900 ..:843 .0397.70.43.84:9438 .9084184:9083.4389./04/.. .9.43.06:../:90/84:943.94383343 /0.9..90/949084:90 .2090770.94140336:/8900   %0724/3.9.9438/0907230/-908900902507.43.9.  . 070 .94370.2.2.5.941.9:70  4 .

943  .9:70 S  %09.209078..430 $(  ( $          (  ( :23:2           04/07 #0..7.9S S   S  .94370..4/078 6:-7:2.4389.3/90/04/07-9006:.39.4389.94381478420209.7.395.7.79.943841403.3.9434106:-7:2 .:08419006:-7:2.7..%   070   .43.-0570803985.0397.5.:.:.30803(  ( 3        $....70:80/147.209078/0907230/147905.943    '.7/04/07 % 8900902507.90789.2090784190/04/.

.% 4.4 .  ( 90701470  .4 3 4.80.( .   390825089.  4.

:80 1472../408349.439.7-432434/0/:73.3/34.943  O ..8989.9:70.7-43890082.14728..088 403 ../0/394970074:58 0/89008 .425090/04/0/89008 84/1.0 4240304:8897:..94341..24:39410.8547489 -4408  O $02 0/89008 3..338420.7-432434/0  3498.47/39490/070041/04/..94341.8938410/8900.% 3 4(  4 (  .943.084184/1.3/.425090/04/0/89008.-08:-/.

7-43.39941-4408  04/..3/ ( ...4./04/0/47343 /04/0/4.0/38900.70.06:.3 8:11.3/403/884.9.02.804:8.890/04/07..7-43890080.3/..9433.7..-06:.0/36:/8900 < .::2 094/41/04/.039.47/3 949006:..438/07.....9433..::2:908.7-432434/0   %006:-7:2.81448   5 ..70 .394198.9070/-44/8:71...79.4389.24:3941.943  (  ( <  070 (.7-432434/0/:7384/1.94380570880/..943 3498417220/89008..7-43/884.O #220/89008 5.

55742.9070/-4240304:8897:.7.943890144306:..43903941343 209.//94394/04/.57088:7041.9907.33.::2970.   070 5  5..9 .-0:80/  (  (  5 ..3/4907 6:.9490 5.79...9:5..:.7089003498 7..9.0397.3.989008  11:843/04/..9.::288902   3.708:9838193 06:-7:2419070.920398:80/1472.889030....9S  S  .70.3/90390..9..90841.70..9:70 4.943 03/884.-4.79.0/36:/8900  /7403/11:80839490 -:--08.9434190 403.::2/04/.92039058947024.083-498900..::25:25  '.7-43.9  '.:8438.47/39490..9:70/0503/03.8547489  '.0/-90..943 ...8 -.3/4...::2970../070133   $9008/04/0/3..041 838:11.738.9203941249038900/0.92485070.. .3/ 40336:/8900   %02507.3:1..808905.-0.7-432434/014723906:/ 8900 14.::2970..0/7403/884.:8070/:.3/.::2..3/90.94341.7-434/..943...707024.57088:7041.43.7-432434/090701470/0.039  47.005708843890403.943 8574547943. 6:-7:2-0900390948890282.943 :--0841.:.3/8.70.-057080390/ -9006:..7-432434/0390.79.90.9432.9438:80/2.9:73..804190.57088:7041 .90/-90.  .

943  0 .  (   %006:-7:2.39419070.4389. (..

0398 $:1:738900 $:1:7 $ 2.0.3.0/403438/884./884.3/49070020398.3.943418..93908.9.0//70.3.9.9 .9.:8438  08:1:7.0/-/0.94341.943418900-30..9394908900209 4/0 343 209.94341908900  .23.9.:8438/43491472  11:843/04/.439.703493974/:.40 8.8390 403.0784:-9418:1:73 84/7438290/ 3..70.943  $3.943 40.707089470/ 3490747/8  /04/.0...  47 .036:/743 0 .90/-343 209.0/04/078390/1:8432094/.7-43 .  0390403.708:983/04/.43.   %:870/:.0397.08900088.. O O O $:1:738900 08:1:7.943 389002.8 08:1:7.:23:2.93908.943.943418900 7 2974504.43.430 .0/38900-0394/11:80 1742908900394908..0397./04/.. .943418900-8.9.43/9438.9434190403. (0 .4894574/:.3/9006:-7:2.70:80/1478.870/:.-0..

3/98-07.//0/94890094.3/.38147230$94 .708 %00:90.147234507.3/84/1089084:-9418:1:7/7458.97442902507.4390393490889.9908:774:3/3743  %00:90.04 .6:/8900.9:70870.-4:9 S S  0 0$0:90.9.3.30:90.9.7088.90/.3.3-4:3/.9S  S   03.:8088.0391472. ..943414 20937438:1/02.9:70.9.97.94341890097.38.3-4:3/..90/.943 #43 47309.9.0.88070..0414 2093743 8:1/088070.0/4984793088  347/0794570..9:7084149/01472.3   . 743.3080.902507.070.9438/:09490570803.75/74541908900 574507908 -79903088 .448/43.9897438:1/08/:7384/1.90/ 17429084:94331472417438:1/0 0$ 14723.   79903088418900.03890-43/3-09003907.9907437..949209.9.9.3/ 3Ø 743.990902507.3080 3 8.

0 ..30802.90/-8:1:7 O O O O :..72094/41/08:1:7.8.47/3949070..9.99 25.943418:1:7   %057450790830.110..0/-8:1:7 2.9418:1:743908900574507908-0.3.9-79908.70-7.943.0418:1/03.90/-090039089007....9..3$. ( .9438  $.43.439..31472.02.9:70412.750/03.  .3.9.439..8. 70/:.:8438.943  $(  .-4:9 S  S  907014709089008.38943418:1:717428900948.:84380850..90 344984793088  &31479:3.0 0/.70037..994:3088 .8.9478/090723030.418:1:717422490389009490-.-.8..8..2.80790.   %02093902507.332.0397.8.82.098( 831.$ .38   90801.08.42082470831.  3 0  95..4/08.7.3.703498.332.:8438439020.00.:8438 $:1/03..9433 8.30808:1/0870.909.708  %030.9...477484370889.098  831.943418900-8.90/..574507908  7.748070.77.43889841  .031:03.38900  %02....750/08 %0.3.0.70 O O O 7990 088/:.-0/014720/34989.8938 8420430841.3-4:3/.38..903$3..43.-057080390/-90.8 %02489545:. .85745.06:.8.00110.30/3 .$   (  %006:-7:2... ..-9   94945 08:1:7.94338900 74:3/-7..842.43907.393.3-.4389..-039.3/ .39$419070.    0   $    3   %7.8.94387024.0397.943  0$  3( 3$  0  86:.704.

.$( .   . .

. .1472  $(    $   (  %006:-7:2.9438  $.9.070 .   %08.3/8:1:73906:/8900 .$.9.4389. ( . .  .$ .$( .90841.3/.39$419070.2070. 3908. $ ..90841403. ( ...943343.

$( .08:1:7174289008.   .8...-941.9.039 418:1:7  $ $ . $ .5..   .90841$ .4011.3/  3908.947024.9070/-90/897-:943.    070 .7..

9. .43.:80823908. .87024.94341.$(  070 $  .8.0/3.9.7./010/990701338..08830.8.389008970.0904/38.  O 30741901..3/340 85705.439039   005/08:1:7..70:80/   94945 08:1:7. $( .//0/941472-.9742.9. 3/:. 03!74..9432.0.00.0/3.  .38.943418900-30.943 897707847.3/ 5.943418:1:738900  8.0/1742908900948.9432.-0.0/.90/39070/:.309.006:.-003.1:73.9438/08:1:7.9.0.943418:1:738.743-:--3.43/:.943-8.0397.-00110.8 %0701470. 8:1:787024.088  ! 947024.0419089002.8.5.8.30259.3.0398 .89773 147. .550.9.//943.43. 8.78174290.-4.82.-941.0./0 %070133 /08:1:73 8.0397.0 99889.80  O  110..0/-.3/903201:8 .2.941/08:1:7.89.03/04/0/ 4 -.43903941.94380110.97.70/.9908900 /:73.  08:1:7.08:1:784 /:094984/0/8.3 574./0  O %0249038900854:70/39490.

..29:708.743-:--31742905474:85: 24:390/390.343 4/0/8.8.  .90/3942490389000907314724154/0797.0398.94190/08:1:7.42-308:5541.-094.-847-90574/:.808 $9773574.43/943841/08:1:7.0398 O O O O O O O O $.3 .94341/08:1:73.743-4394908900974:.439.  30.$ .      .9..3.3/8.943-30.0398.70:80/...0473147241.7030.943 !70803..02.039 54/07 9 89773-.907.984190/08:1:7.9432094/8:8:...039 390.      .9478 O O O O .5.30..943 70.$ $   %014432.8.0//:0949014431.9.0./0-499428:80/   .439.  20 ../344/309.9.943 .5.039894.3854790/-. .-09003908900.24903890089024890110.3354/0741 /08:1:73.743-43   005/08:1:7..8/08:1:73.70.0398 .94341.   ./850780/08:1:73.0.9.        %0/08:1:73.70.   .943..02094/418:1:77024.99072094/89773-.470/70..041-...

-057080390/ -90144306:.  02.0398.0/389002.$    $( $   30..9438-09003/08:1:73. 4.3/8:1:7/884.94341/08:1:73.9438418:1:738900   .70.0:97.4894.43.9438  . $( ..0397..0398.0.

:843838900 7 2974504.:8438.  43 209.3.70..8 $    43 209.-9 /:.039  %50841343 209.3.:8438.3.3..8...0/38900   4034:83.3.81:73.4254:3/841209.043908900 574507908.9:0897039 .477484370889.-9 ..9438 /04/.  $:1/08 0$ 3$ .:8438 O /08  0    $ O $  3 7 09..:8438   3/034:83..     0 7  0    3 $ 09.39 0110..908 48:1/08 ./0/ 3949474:583/034:8.943 -0900390020398/884. 70.:8438.-9 0503/3439084:7.:843..:843838900   900079831.343 209.02..0/ 90..0 1742.84:7..5.4254:3/ 0 /11070394/08 4/0 8:1/0 .088:.02./0 33 24/2.:84381472805.0/.8 O O O O O O O O %0380897039 01472.$ 0$ 0 09.:8438 85308 8.7.:8438.70/07...43 209.70.4250 343 209.808 .70/07..7-4397/08   085904182.  .3324709.3.3430.9439089005745079088:.. 24:394104034:83.905..708:-/.708:941.8 0 3  $ ....943 /08:1:7.07017.3/04034:83.7014720/36:/ 84/10/4784/8900.43903941343 209.$ $ 0$09..7038:11.907.439.94708 .3/90731:03. 9343 209.0/174209073.-9 !48.809.99  %4:3088 .808 %0343 209.3..3..  O 8:1/08  3$ 3  .0 0/.3.

0  %03:..:808..943574.03:.94347 /08:1:7.08..94347147.9438/0907230/-900993.3:.:843.7-4397/08 %9.9434190305.7-/08 0  7 3 009..9:7.  O .3/908:-897.943 49434190249038900/:0949072.701.8090305..03.943 20734184/3.43.7-4397/08 34-:2.7-4397/08 .903.94341343 209.2.09038434390-4:3/.-0709.943  749413..0..0903843 904078:5078.943 99889..70970089.943  :.805..  O 97/08 %  ' 09.9432.943    749 74941.0.:8438 %0.9:7.079.08 /04/.03.0.08413.:843 0993.  %03:.80 49073.80 3:.73.08882:.3:2.47.903.:8438 47 .4207.0.0.4.943574.94370.8.08890701470.  O !485/08 0! 0! 3! 472.06:-7:28.30/ 0 2.:8438 .708:9418:5078.0888/0907230/-8:71.O .7014720/.:84381472.484384190 3..0784574..08.30-09003.4207.9:7.80.443/434190209.9:7.803:.3.041305.7903890    4.-01479030 5.807390570803.943419084:943 6:/ 4784/8900 99084:908 0 .43/943 40993.08.0.0:8 .//9.041343 06:-7:28:5078.0.0 2073416:/3.:843 6:/8900  %0088908:71./:2.:8438 390 209 398.03.02.0398 47.30.:8438384/89008.04149075.801472.30 .4.9438706:70/1471472.0.0/ 34 8:5078.4393:08:3990..3.7.7-4397/0809.708:93907.:8438 %070.0/89773.3/..3/ /:094/884:9434190..0.

094207003.3.007.39082.074308 %014.4/0  ..943574..-03903810/-24/07.933.89079.0-09003903.804190-4:3/.703.0882.:8438.00307.-847-0/-90 8..4207.03- 90030709.3/ 906:/8900 3.:843..9089773 '474:889773708:93 .0888/7.78:71..:843814.9:51.70.:84389078:71.93574.-030194-9. %014.70.30/1742/0.

/745098.390.-70.703.:843839482.

.7.750/08.3/48:1/08314724193128 5.708:9419071472./0/0.:8438.:8438 805.5041343 209.70 2.70.5745079088:.:8438.70.503.0397..99 94:3088.:8438  O O O 897-:94341343 209.90 4984793088  03/7908.:8438 .:23:2..:8438.0....90098.3-4:3/.8041/:.3.9418900 $.:8438 08/0841908.708  $:..08-09003 90/03/790.7-/0847397/084240304:8/897-:90/3908900.3.79  !40/7.32.:8438.9439089005745079089.708:934.94.7088:3/087.90/  %0803.3/.574507908 418900824/07..9439020.30808:1/08 .50/3.:804.439..8.39..947/090723320.897088 ..9:0897039  O O ..0/- ..908.3/8.94339085.:.:23:2 4182.3/8:1/03.50414-:.:84382.90.90/-5:75480347/07943.-083.438/07.7014720/.70.702489:3/087..78.-083.09895041 /897-:9430.2508414-:./.-0 %0..-8475943-908.:84382.50/3.::2.09070110./74541 20.3.9439020.3/1..:23:2 ...17..3.83 .:8438 4754441/03/7908.438/07.9:0897039419089005.943 36:/89.-095041/897-:943  38420890082.-0.381472.79 0 .:8438 $9008/04/0/-.943-.73.700.24:398417.3/48:1/0814720//:7384/1.  :89078413.33.-/0.:8438907/897-:943974:4:99089007. 433079.  0020398 :09490724704-:.:8438.//943 .1907/005/04/.3 897:.943/:7384/1.90 $507.:8438.0  47'.50/3.3.50540/7.0902.50413.845742490903.43.728 743..-02574.020935439079.708:9410:90.8-:--0824.748.908  !..3-4:3/.90..734989..70.088.50/4/0.79.9.79 .:23:2 708:98 31472.57450790841908900  O 4240304:8/897-:9434182.-083.3.943413.90098 4..:843814.3/03/7908..:8438 O 4-:.97..3.93.:84388902489/087..9434139073.94341/03/7908.0725479.73.84:31.894:3088.708.70..50/3.90/.0.3.439089007.3....9:708.3.78.:23.:8438 00790880110.43907.3078900  4754441343 209.47. 47 .3:5974:90 249038900.43903941.03907..3/1.5745079085.20398 .:84388.70 .45.943  !. .90098.3/0079.50/3..8.24:394189743/04/07 .03890209.3.3/.3/.391.3.07800110./0:73.300.30808:1/08.80908900897039  4.:84388570107.47307841 90/03/7908.8834189003708:934-9.3 -4:3/.3.

0/ ...  %5..02.941906:/8900 0.3.209.14723 0 #43  :.480949.04308 O 4304182.3/.903.3 94805. .99.-0/70.7.749  ..3/043..4/ 209..708:941209.789.:8438 .90/390743/70.24/ %0.943 06:.943 /05708808903:.425489438..903...43889841 1.38708:9..074182.47.384117.9:70410/8900349 7 2974504..38.20398 43.789.943.349897:.:8438.3.708:941789.06:.0341.0780/70..943.90/3.3/4907574507908 0.3/.41.8.704079.30.0/7..7879..0..38 . 897-:94341343 209.943  $97:..943 %0088/:.09490743/70...:8438.90/.81472803.439.3.574507908397.70/014720/.8.314723.420894...384974541 20.9:70.38 %093.70-70.8 7.:84382..3/907..9-07.

.0 800/.0/6:/3 90.70.0.708:9410.38 70..90/ 54..9434190.38.0/-9025:7908 8:1:7 5485474:8 .90/ %8430 147280390100/34184/13209.50/4308.3/907..439.039949084/1.808/:094901443.4:23.50 .29:704182.70.7..9097.3/9024/.8 84.. 472.0/7.90/1742906:/544- -7/08 147290743873. %0.:80/-84/1.3/4..388037.20398 .430 8.9 97.89 547943416:/84/108 %024//08384:/574.7/8/70.9 98.3/9072.77..789.943  0390902507..6:/838:11.70  43041./.77.914 4:23.9434106:.99043041873.24/.7006:.9434190.77.0/.9430 $73.70/9419084/10/209.901742 49073494308  49942...3/.94390701470903:2-07413:.789.38 %8574.4304190349708:931472.0/7.708:941 873.84.808/:09490 -07./0:5.3/./039 40.89.054748984.0 .9070/-30..0/7.99 .7.0 0490873.06:.098416:/209.58..90/0.O 43041.9:704190209 .943.38749 8945  O 43041.708:94190.38 4902507.9:707.0.907/8.039 84.8.7.4393:09474:39900.054708  %024/8.94317439 3.8/073:55070.943389003498 .08..9434184/1.7-43  O 49942.4437.8.088884/:094 840.914 /0.-0.77.90390.914 .43899:943.3/90.90419084:90 037.0547489  .:808 O O O ..4/209.0.3.-4994241.4:23.8.789.430 %8.08070.805.5-0900390349.38 4:23..79947403.38107974:904304182.06:.748070.794190349 .817.3//70.8..9 .984.38808 . 0..0/7.037.44303/.7/0/ 070..:3/07...4794 /23890873.9.914814720/.90/3909455.9434190 49945 1.80/239.939024/.4308...908 873.7006:.4:23.-90708/:.8989.77..738743..3889.7.387498 4558909490/70.0.94341.943410.943419025:7908  O $3..

943 .:80/-90700...4394906:/5.9:70  !.9438.0/99084:90 %06:/88:774:3/0/-90 84//03/7908.943 413:2074:882..0782039 30.748070..9438.708:941/110703984:-94125:790836:/.  $4/1.0/ .9.2039 5489.748070.808.:.:808412.943   $070.80  %8700.3/84/5.743084190349.943 415.84/10/.7.748070.943  .084.02.943 84:90 5447   %7.748070.805.8.943419084:9081742.8094..748070....799434184:908-0900390/03/790.43.94341.4   $070.0397.804784:90 544784/5....3/3907/03/79.7 2974504.9070/-.9434125:7908.3.0 2.3484:90.9438.748070.48..88708:983037.0790 84/132..:80412.38107419084:90 7.503420343.6:/5.79.943 .70/89.728.6:/8.7.943890-.4300203983/1107039704384184/10/ .0/8070.6:/.943708:9831472..990 06:-7:2902507.748070..3/.943 47254.4:208416:/037.

147.4.708:941.802.0 390/70. 24.3/84/5.24.80.3/ 209884/5.:80/-9014430110.89399084:90   %02.943  O 43020930110.  O :4.8082.9:70 %0. 897:.0.9:708.7424.7.4:2084/108.7..9:70.990499078/0034302093  O  -:--08 .9:70 %024./0394190/0389..8.9 805..0397.08 6:/5...4:2041906:/5.98 O $4/1.02039841906:/.04184/13..43.943419007902507.:80/-7.990.3/1107039902507.80.36:/100/8908733209./039841 902507..4/078/0.-0.99845548908/082.3.3/84:90.0 $73.:8088:.94341906:/5.943873.80974:903907/03/79..90.

.147..70.079../0 94 24//0.0/-00.3/17./0  $4/10/209.-0.93.8900349.24...:8024.748070.08070.8977078 . -:--081472384/138900.84147.0..884...943  O $0/2039.90/36:/5.748070.9.943 ..08 09.3/9074.789.10/ 20.-7.80 $4/.::2  4.9434184/5.2039841-7403472090/411 /03/790880990/43 90.84240304:83:.9438.4  O 9073..943430838900349  0.8-:--08..974 2.:80/-90030741908970..02039419084/13.422430.708:94109074.020392.43903941209.8833.-0.2.94343083.80.36:/  .0452039412.254:70/3949024/174290.309.3897:./04/0783 7220/890047.9:70  O 4994230.70.90/9 903497.8.3.

08808 855.798   09.943 700.8.3/49070.9080384/108  O  8070.38.43889841..99.94389.789.9498.90/390945.3497043-0490873.08808 .9431743957470883 17429024/..0397..198 3:..943 %0.8.4994230.4/209.7.3   $4/1.7089349  2097.5341..708:941484:90.789.3894.50/84/1.90/-9084/1.430 %0-49942.9  499458070.708:94190..20398 .6:/8:774:3/390.789.439.430.39/0.08 147239043041.74 /010.943 /740338900 .8574/:.798.344:80/14713.:8438 .94341.03907 %0.38943174290.7006:.  .430413498037.3/ 2.3..84/1.38 .3/..0/-8:1:7 .9:70 O O O 43 209.7089003498 7 2974504.3308037.425783-49942.54075.0397.0397.0/3 - .38884:90 7.-4994241.0/- 9084:908.57088:70..80/239.984190349897:.748070.4:23.9:70 .908 170..943.70706:70/1472.6:/037.3075. 06:.817...4308..757088:70..0397..9070/-9097..943-84/13/03/7908 1440/- 503097.74.943814720/.0.748070.943390.990704389897:.0/..8.9438.4:23.7-43 548547:8.5.90174249073494308  O ' 8070..9070/-831.738743.1472390.3/.04184/1.02.814720/390 0.3:1.399:7-308.77.908 5708039.789...9:7300.24/.94343084. 2.947 749478.0/984:90700.7034988473   %0.08070.94341906:/974:90/03/790800943  .97...94317439 %0708/:.708:9412.702..29:704182.198 0307.0452039412.9.99013.0174290708/:.943 499458070.7..0/7.77.0...-7.943  8070.7006:.0/7.3/914728' 8070.$900  .80990 /439490' 8..7089003498.94341.38  807.0/ 7.3/490725:7908  O 499458070.7006:..3/ ..884189008.8.43.8.9438 ..

9:0897039 ..:843838900.7-4397/08 4 !485/08 O 3.-9 !48.0.3/ .:8438 85308 48:1/08 ../041 .97.:8438 43 209..3324709.08808413:.70..8 O O O O O O O O %0380897039 01472...943 749..0 0/./0232:2/0700418900897:.43903941343 209.3430.0.706:52039 00.02.:843831:03.89745.39 0110.42548943 4/08 8:1/0809.. 3:.808.70.-9 /:.20907841343 209.0/ .  4 /08 4 $:1/08 4 8:1/08 4 ..-7.70..94384:/574..9..7-4397/08   0859082.98/0. 5.98  43 209.7-/08 4 97/08 4 ..3:1.439.08:.9439089005745079088:.:843838900   900079831.808 %0343 209.:843880 $041343 209..3.9:70/010..703498 1.7..:84388/0907230/-90574. 54075.4254:3/ 0 /11070394/08 4/0 8:1/0 .3.34441.:84381472805.03.-941905.3.8 $    43 209.8549039..4250343 209..3..8 0 3  $ . 5.7.0..809070...4254:3/841209.3.3.792.4.06:52039 .7982.-9  %014435.02.04390574507908415.708.905.9:70/174290349 $3.3.477484370889.-9 .79847306:52039 1.3.:7041. 9 343 209.398 ..99  %4:3088 .02.307 %0.7089003498 O 02..%0897:.3.08.9:70/010..

3:2 .:8438 .:23:2 8.50 247544 41343 209..03.00307..94341903.478 .08.943 8:71. .3/.0.9078:5078.:8438  O $.4207.943../:2 09.9:7.943 419084:908 403 8:1:7 397403 .:808903:.3.3.43 99.4207...3/1.4.0..

2039841-740347 2090/411/03/7908  O .50/3.7/ 3.943 %014431.94341/01472.70.3/17.8902.90.789.48079406:-7:2708:933/0.70.9:0897039  O !8.3/20.:8438007924/07.3/7.8.748...7.0/ 99084:908700.38  .20398 2.:80/74541908900/:.0902.70 :31.0397..94.89.43.574507908 .:8438 .45.94781.0 -:4.7/3088  :.:80412.:8438043.:8430079.3/ 1472.:89078 .0397.4 4-:.3.50/3. 84/1.:8438 -.90.79 .9434189708808/:73 903491473.6:/.707 85..708.943/:7384/1.894:3088.7.8041/:..08 .9434190/03/7908.799434184:908-0900390/03/790.38  4240304:8/897-:94341343 209..439.943 8900473 :.//9434189743/04/078.43/9438.50 8.-0  4 !.94190/03/7908.94341..24:394184:908 8:1:7 5485474:8 .708:9410:90.3/-79903.4437..039.94341 84/.90/-9024.3/.-84:90./7454120. 80/2039....:843147236:/89.9031:03.3.3..9417.:23:2 %078.0/99084:908  !.70/89.78.4437..3.90/03/790.-0 :89078413.:8438.79 0 ....72475448570107.791.0397.40.90 3.3/ 1.   0020398 %00110.90098.20398.943 !.3/072.8083.3/90701470982475448:3/087.:8438.07..07800110.94.748070.72810/9906:/209.90390/70.7-/08 397/08 8970390390209.728.4782.708:934.7/3.8.9343906:/209.08..73.3..799434011.941540/7.3..43..3/84/5.70.5745079088:.7084:90..99 94:3088.9070/-8.9:08970394190 89005.3810770/ %7..:23:2  4-:.4437.47..94341.748070.:84381472...38107416:/.:80.3 9..943 79903.2..748070.9..037.390.7-43 $9008-03037.3/805.9433..90...904190209.80..70..:84382.300.6:/209.3.748070.789.50/3.090708/:.9 43908900574507908.147.99 20935439  .08-0900390/03/790.84/13349890708:9 4184/1.7089003498 .90/36:/5.9994:93.50/3.:843882489/087.90/174290349  4 !40/7./01472.0.943 //943.50/3.7/3088 /:.9.:8438  O 897-:943 4240304:8 .0/ .439039  O 4.-7.90098.3/90717.3/3907/03/79.9907.-083.943  O .943873...943 .943. 97.9431743990701470.:84384390890057450790880889.748070.43.3.:8438-0.750/08 .503.94389..3..6:/8.3//0.90708:983.84240304:83:.70708:94124/1.381472.3/1.70.384/1..0397.043908900574507908 907014704-:. 84/1../.:8438-70. 47.80 416:-7:2!.349430 4.-097.0/1107039/:735.-0  4 03/7908.99013.700.804190897039.:84381472.707.3-4:3/.

430.3308037.08 147239043041.908 170.70.38884:90 7.817.80/239.943 4994230..38 .9.0/7...8900349.884.0/ 7.4308. 06:.789..4:23.50/84/1.0/984:90700.045203941 2.24/.708:94190..77.0/7..0397.7006:.4:23.430413498037..9431743957470883 17429024/.04184/1.8.425783-49942..748070.80990 /439490' 8.-4994241..9070/-9097.3/490725:7908  ..90/9903497.9080384/108  O  8070.7-43 548547:8.9438.9498.789.430 %0-49942.3/914728' 8070.94343083.3 897:.738743.77.3/ .0397.3/..38.38  807.943 %0..29:704182. 0.708:941484:90.43.3894.990704389897:.8.943390.6:/8:774:3/390.7.20398 .943.0/.908 5708039.38943174290.9:70 .9438.814720/390 0.3/.43889841.0/-8:1:7 ..90174249073494308  O ' 8070.4/209.9:70  O 4994230.7006:.94317439 %0708/:.08070.03907 %0..789.789.08070.3/9074.99.439.943  8070.0397.9.90/-9084/1.7006:.

30 .90 .0 .70../:2 99.84.9:70708:9833.7089003498 O O O O O O 4073.3:2 7.943  /740338900 $4:7.90/390945.0841/740336:/8900 O O O O O .70./07013389.943 /7403 /0.943814720/.041 8070.0174290708/:./089407. 89.7-43 3.0 .943(( 5485474:8 /0548547.-4:9  $(  4.43 .0/1472841/74030079.748070.9:70 40754:73902507.84:943   .943708:9331472.883 $900147 .0.943 499458070..943-84/13/03/7908 1440/- 503097.07800110.9478.3 418:1:7  41 5485474:8.:2/9 :0 1:80/  /740380./.0397.81.94341.3.94 4190349099498/.94341906:/974:90/03/790800943   .//9.:23:2 9:38903 ..2090784:/-0.9434190349/2038438 140.42243.804:8/74031472  384/8900/74038/884.90 $4:-941/7403 38900/74588.43.33107790   49.4338900 .3/8347/07947024..57450790841 89008 .0/- 9084:908.39.943 700.748070.-025:79088:.94708 9248507.94389.742:2 :594  .4:2-:2 9.9433.:89039082:.4394/2382..943418.:2 3.24:3941.43:2 .90/ .3497043-0490873.84/1.9438706:70/907..742:2  .79 0 .079..90/39020931:73.4437.88:1:7 /08:1:7.258.3.9  499458070.80419054:73902507.-0147/05708832.8.3/3..0/36:/89003/884.8041 90.. 00203983..3/:59455241/7403  43418900-.94320..70.7-43.70..439.O 499458070.  477..809084:-941/74033 84/8900  $4:-941/74033.75/:7384/1.708:9412.43.94343084.47./07017..3//884.942.0:3/087..-4:9    0.7089003498.43903984125:7908 $900147..3834924709.3/.99013.7.0.0/31472413907899.0397.08 :73...6:/037.3/.809084:-941/7403384/8900  $.8/884.748070.804:8.439039  4/1..3/07 /0.-4:9   &8389007.7034988970.700.5 :08.85488-0 ..

939073...943418900-209.939073.3.99 7.08 $4:-941/7403/0..3/1.31:73.703498 '..9.8343 209..857088:700..0 20931:73..70.9428.:80 1..43903941/740394552 .-4:9  3.0.0.920394189003.8.40.7.8.42580/-9090.883 '  .08 0390.7..94341.90/1742.0885.:89078 873.4/88:. .9432094/ 0 ../0-4304190/0.O /74031.443/43418900349 /7403 .943418900 94.:.8832094/8#0..7034981.0   3..943 0.-4:9  39020931:73.943-30.8834507.0   04/.90/.::2970.883 # ./0:73.8/:..8090..3/4907/04/30020398  #024.4/8...0/1472.70.84/0.054708 ./3343 39072990398:55416:/8900949054:73 94 24/4507..-7.89708808  /7403.40...:84381742906:/89003-4920931:73.0  08:1:7.:23:2  8..:.0.31472.943  O /740302-79902039 /74033/884.020394190706:70/902507.41343 209.2..0398  .70.3/907..70.0.94285488088324-9.0397.943.8 1./04/0789490706:70/..70.79.-7../00.943   %05488-090.-7.34441.8832094/8.344.3074:81475.43.42-30.804:8/7403 .43.3/1472./0/08:1:7.::2.943 94.3/ .00/8908900897039  /74031.9203941908900390./0:73.88.-7./408349.020841.::2970.9:70418900-0147054:73949024/-:83 .9:70%4:3088 .7981.7.80889005745079088:.3/  '.7034981./0 /0./07013389.:801472.3/903-..:80/-39073...943.:8438 8:1/08 4/08 .80/:7384/1.7057080390/3901:70  .3.943  !74.943 O O O O O O O O 0548547..94341.90/.943841.494/0.9:0897039  %0../0 70133/08:1:7..89002..34441.7/../0 94 24//0.70890034981.943 %014439..3/...

438:2.75943 ..97.90/-.249038.08841702093..9748.9 0307.#02093 7 2974504.847:2 0.3/.574.:8890.86:08943834:7.974/0.883974:.#02093 $# 8.-090039000.  0.0.:770395..300.088/08.  8.907.9748.3/90 84/13349  $#574.974/0:93900.79.-000.

79803904079541.702093574.8.  %05702090/8.974/09580.8 .7989420914723/745098416:/209./041.883974:90908./8.917429000.:77039 .4330.3/83974:908.907 .90/-90498.7982.70.438:2.90/94.43/:....54078:55  %000.90/4390..390209354394190702090/209.3.9:70  .97.5488088300.9902507.97..974/08 220780/394.3/7.07  .984.9.-4:9    079.3/89..54441249038..-000.42243 5.%0.440/24/-.494-070209  300.  %000.4330.-000.00589.  .974/0.5..088 $# 89.974/8.89471470/.9748..80 .438:2.

9:70 4$73.198 0307.3. 9438.7./3 5:798900940.9/:094.#02093 O O O O O O O $:507.90 $4/1.3/8 3498:594 2097.3/873.94190702090/..4 #06:70/0.70:80/1472.5.08410.3/4/08  %0/74509803907890249038900544 -4994241.41343 209...85747088....:21:47/0 .9438  %9.9:708  .489 #06:70/0.-0574.-994.3:2  .3.943.943 70889.8.897:.:23.9438410.06:..9437.#02093 O O O O O O O O 005/08:1:7.7.3//08.55.8.974/095.3:5.9902507.. 20 ..34408574.80/43.0.088  55.. %08.702093 $# 200989080/02.03/3/745098.4.-7.3:1.3/7024.:8438 8:1/08.4854880883897039 700570889./03941902507.339:7338.702093:9382:9.:8438 4240304:8897-:94341343 209.9748.5.0.5702093 %93./08901443574507908 O O O O O .943 14723 84:3/4240304:8209.3...974/08 %03498.9 84:-9418:1:7 .80.39.0412.97.04.304:870209341903841 00..748070..7089003498706:70890.93:398 9:7-308.94341.907 .0739  /.70574/:.3.3//089008  $9.43/.97.43/:.425489438-.080.943.3:22.94317439824.12.3:28.98 9908.44/8:71./0870.308889008  %9.42548943574.3/14:3/78.943 44/8:71.938.3:2..0547489 %0 90.9:730.    09354394079.52.5407 0307.9.704733498 .3897:.:8438 307.79814700.04100.9748..3/0970130//:094/08:1:7..07.0.4550724/574.9:70708:933 84/1.799.-0 70.947749478.440/.9:70  %0349./3...0-.9.439.84/1.0/010.0/-$#574./847-343 209.3/4/.48 3..7/8 :3/70...9748...9 43974.98 42.198  #432748  %44.943.3444100.3/.07485.0/-00.748070...4890110.%08.06:.48147..9.39..9748.:8438  %02490389003147241-496:/12439000.943 #0133343 209.3..3..084/13 %0 .

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

-8:71.4170/700.34/08.0-70...70.09490902507.8.3/0274:37432 #4:74328 2.943 %08975902507...0 $.931:73.431:7.07:908 57088:70..94394..0.0783479.708:9 41902507.9:704/.907098/70.943390700.931:73.8..9:70/0..90/94908.0-70.-8:71.8083 9074:7434507..9:70       O #024.0090794 4714:7 .03.07 7434/08147243908.0  O #4:7433090770.-4:9     O .

90/3.330070904/08.3/0214:7 7432  89.94341908975 99889.090.70897.907098 %0902507..794190897588:80/3.9430  0   #383.33.      O 43901380/8975 49740/89758.938..80/-.0417434/0843907 8:71..478:1:7.47/3949070.439740/3984507.47.88.943  O 443-./708/:.43/943  9075..43  !.34189008975 49740/89758970.../ %0.0/942.70.3/5.9:70870/:.0 !.0. 5.3837433.3/8 %08975/2038438 9.798574.0/  O     94945 !.0880/3.5..330 O O O O O O O &3..94312814720/439089758:71.8 740/.907 1742908975 !...84:94341/74.//884:908904/08.0../3...0 17429089758:71..43  ..0574.943  73  /097223  3  #0.8.4774843 57490.9..88.9.3088 /9 .087024.

.93088 .99419089009.3708:98370.43/:..3  O %02507743 835.0841...0.9.314:7 .0138 2574.92485070 .789.439740/70/:.9073.3088 2574..0 ..7/3088 0.9.:/0890144389.3/97403 570.0407.8808.3390005/7.0883.3/8:71.943 94.330.0203941908:71.330.943419089759..088   %05:75480841.9..7094..9.574.88743  13..4907390-09501:73.9:70      3.7/033   4/743574..943419089007.08833.4/7434507.4894 .330.330.330.902507.7994908900706:70/0.3/8.7089.439740/8500/ 390-. :5748.3574.70:80/2.4393:4:8 .31:73.0 330.3/3 8970887001 %070.431:7.9.31:73.33.9434190 89008:71.9073.3/027432 %07432.9:70.3088 70/:.47748  O 330.0138 4:7 74328:80/1479025073  O ..330 800905.48.04147.3..01.033088 .3/-.706:70/0.9.330.4/743574.4393:4:8..3897:..08889008975 .7/3088.43889841 89..0/43945410.90/347/079425.29:7041/7403.0 390.9:70-04  890089755.03934/.0841.9.9.4393:4:8.3.0.943..0203941908:71.70-..0.943949.0203941.    94945 4/7434189008975 4/740/890089758.3/9482.08 4/7433.330 .0.3/07/:.42243.70 O O O O :790770/:.3574.3 .088.330.

7/30884153.7/  ' 6:.7488-70.38 .7907.43/9438 .0.7/ ' ./4349 ..43/943 03/3.0/89002.7009.7/  '    ..34507.330.:801472.7090708:9414..48941..7907.0889758:71.88 574/:.943-043/900/5439 9902507341 .7-43890089758.4//01472.5.709025070/83.330.94341.43/94384189008975.38 .9434138 .07897.07897.5.0/ 89709.:80 1472..-4:9 '  907902507.94.090..330.0/4.3//005/7.0/.7488-70.0/8975 343 33902507 53.8 .709448419 ' 3 .880/89008.1.8..7/  ' 97006:.9438418419.3/89709.341908975.330.3/89709.

33-749..70 7024.943..439.42243.203..3/7:89.-:77..02.3/7024.20/08 ..0/.7086:.3/ 20..47/3949070.7049/5.-9419074:8:71.70/0/08 .30/0..83 .439740/0.23.4393:4:889008975.3/7.-014703..9:7.9745.9:7.20/082.74 .9913889758.30.3/5.93.8-0037024.0.-7:808  .01388574/:.7/033  O $90/08 8.9430  3  0  3    O O 3..8/:094343 :3147247.75-:77  O 70880/0/08 890/08 1742.-..0138.39448 5:3..33 /070..0/  O #40/0/08 ...0/-749.314700.389755.33574. -...4/740/8975  O .3.4.0..03.3 070.70 /884.33 %84507.7.3/.0  O  $9750/08.0944/:-7./3417.790.088./.80/.9430  0   #:8970.44341-79138 8975708:9331472..3/:09490..  $:71..0/17429089008:71.42-308.3/90/7.99 /: 8:71.088:9.4...4/74394:9.93 %02489545:.70574/:.43/943841.33.73.0/-/74.70708:941.93 49.5.70.84:80/3/005 /7.36:0841.3/7380/8975039078.93.0/-.0  O !..99 8:71.70:80/2..93   49/5.3/4907.43/94341.789907 $90/08..9438 7434/070.088 O O &3.90704/08.4.7014720/-0/0743  O 94945 $9008975.43  0.8808974:.99249033..01388574/:.39574.33 0. 3  530.0/-743-090031305480/748  774713889758.9745..43/9438 .709 898.0138.9434193-:04/012439089008:71.99 .398.3-..42243 8:71.47.-.....3/ 0.943 -09003908975.93.4/740/89008975 7747 $:50747:8907277471388574/:.34/07 /0  O :0/ :0/8:71.943  .0/-743-0900374:030/748 .0/-743-090035480/748 9890..08  ..:9934507.393 .93  O 79 791388574/:.

00..43    .80/.98 %0 89758.93-.094908975455489094988:71.00.0..3-.943.O O O 443 %0.0...94/0 30.0882449..7.3/1.9745.34/08.989758:71.93  O #0.0 .088 O O &3..98 10/9.23.389755..425489438.30.84:943 0.9745.907  0.9745.0  O !.-7:808  ..93.398.33 /070.440/-.8.77.90/89758.9430  0   #:8970.0 %05489./.97490..43  0.742:200.4330.0/-/74.9.4330.93574.4.3/7380/8975039078.47.300.47/3949070..400.70 /884.93 3..007574/:.907.0/.9745.3/7:89.90/.70/0907230/ -9090/054890/2.3/4907.3/7024..83 .3/.9745.9749.932094/ %3.42243.93 0.8070841.3/.9745.9...8808974:.079.93  0.3/ 20.33 %84507.0  #0.90/949054078:55.70 7024.33-749..90704/08..34/08.0.93.9430  3  0  3    O 0.7.3 070.03 0.30/35.47.439.9745.742:200..9438 7434/070.9745.3/7.42-308..43   4393:4:800.3/9000.0 %0-..70.3.0/17429089008:71.5.

3/.86:08943834:7.847:2  .907.79.0.:8890.  94945  8.

Sign up to vote on this title
UsefulNot useful