PRINCIPLES AND PROCESS OF POLYMERISATION IN PLASTICS PRODUCTION





Condensation polymerisation and addition polymeri­sation are the two main processes in plastics production. The manufacture of plastics depends upon the building of chains and networks during polymerisation.

A condensation polymer is formed by a synthesis that involves the gradual reaction of reactive molecules with one another, with the elimination of small molecules such as water. The reaction gradually slows down as polymers are built up.

An addition polymer forms chains by the linking of small identical units without elimination of small mol­ecules.

The most important concept in condensation polymers is that of «functionality», i.e., the number of reactive groups in each molecule participating in the chain build­up. Each molecule must have at least two reactive groups, of which hydroxyl (-OH), acidic endings (-COOH), and amine endings (-NH) are the simplest.

Hydroxyl is characteristic of alcohol endings, combin­ing with an acid ending to give an ester, the polymer be­ing known as a polyester. Examples are polyethylene terephthalate obtained by reaction of ethylene glycol con­taining hydroxyl groups at each end and terephthalic acid containing two acidic groups and polycarbonate resins.

Alcohols are a particular class of oxygen-containing chemical compounds with a structure analogous to ethyl alcohol (C-HOH). Amines are various compounds derived from ammonia by replacement of hydrogen by one or more hydrocarbon radicals (molecular groups that act as a unit). Esters are compounds formed by the reaction between an acid and an alcohol or phenol with the elimi­nation of water.

Bulk addition polymerization of pure monomers is mainly confined to styrene and methyl methacrylate The process is highly exothermic, or heat producing. The dis­sipation of heat (necessary to maintain chain length) is achieved in the case of styrene by intensive stirring of the viscous, partially polymerized mixture, which is then passed down a tower through zones of increasing tem­perature. Alternatively, polymerization may be com­pleted in containers that are small enough to avoid an excessive temperature rise as a result of the heat released during polymerization.

Methyl methacrylate is also partially polymerized be­fore being poured into molds consisting of between sheets of plate glass, to produce clear acrylic sheet.

Ethylene is polymerized in tubular reactors about 30 metres long and less than 25 millimetres in diameter at pressures of 600-3,000 to give 10-20 percent conver­sion to low-density polyethylene. Residual gas is recy­cled.

Polymerization of monomers in solution allows easy temperature control, but the molecular weight of poly­mers formed is reduced because of chain transfer reac­tions

Solvent removal from such a solution may also be very difficult. The process can be applied advantageously to vinyl acetate and acrylic esters.

Suspension polymerization producing beads of plas­tic is extensively applied to styrene, methyl methacr­ylate, vinyl chloride, and vinyl acetate. The monomer, in which the initiator or catalyst must be soluble, is main­tained in droplet form suspended in water by agitation in the presence of a stabilizer such as gelatin, each drop­let of monomer undergoing bulk polymerization.

In emulsion polymerization the monomer is dispersed in water by means of a surface-active agent (a substance slightly soluble in water that reduces the surface tension of a liquid), its bulk aggregating into tiny particles held in suspension. The monomer enters the hydrocarbon part of the surface-active micelles and is polymerized there by a water-soluble catalyst.

This process is particularly useful for the preparation of very high molecular weight polymers.

Exposure of certain substances to X-ray or ultravio­let radiation initiates chain reactions that can be used for manufacture of such thermoplastics as polyethylene and polyvinyl chloride.


RESINS

Resins that cannot be softened by heating include the phenolics, furan resins, aminoplastics, alkyds, allyls, epoxy resins, polyurethanes, some polyesters, and silicones.

Phenolics or phenol-aldehydes

The important commercial phenolic resin Bakelite is based on phenol and formaldehyde. The two processes in general use are the one-step process producing resol res­ins (the first stage in the formation of a phenolic resin) that are either liquid or brittle, soluble, fusible solids, from more than one molecule of formaldehyde per phe­nol molecule; and the two-step process, using an excess of phenol to produce novolacs, resins that have no reac­tive methylol groups and must be mixed with an alde­hyde to undergo further reaction.

Resol resins thermoset on heating and are used for adhesives. Novolacs require a further source of formal­dehyde in the form of hexamethylenetetramine to pro­duce molding powders. Both resins are run out from the reaction vessel, after removal of water by distillation, and ground up, then compounded on heated rolls with fillers that vary from wood flour to mica; for strength and heat resistance fibrous asbestos is used as a filler (hexamethylenetetramine is also added at this stage in the case of the two-step resin). Final grinding produces the molding powders, which on further heat treatment will yield the typical thermoset resin.

Phenolic moldings are resistant to heat, chemicals, and moisture and are preferred for wet-dry applications as in washing machines. Their stability to heat and low heat conductivity suit them for use in appliance parts, and their electrical insulation qualities qualify them for electric fittings such as switches, plugs, and distributor caps; resistance to hydraulic fluids has led to their use in automotive parts. All these applications have been made more economical by the development of injection molding and extrusion methods. Complex phenols are used in manufacture of brake linings.

Furan resins

Furfural is a five-membered ring compound (i.e., the basic molecule has a ring shape and contains five atoms) of four carbon atoms and one oxygen atom, carrying the aldehyde group, — CHO; it reacts like formaldehyde with phenols in the presence of an acid catalyst to give a rigid polymer with high chemical resistance, used for coatings in industry. It can be prepared in semiliquid form with a low viscosity and remarkable penetrating power when applied to porous forms such as foundry sand cores or graphite blocks, being in this respect superior to other liquid resins.

Aminoplastics

Urea resins are made by the condensation in aqueous solution of formaldehyde and urea in the presence of ammonia as an alkaline catalyst, giving a colourless so­lution to which cellulose filler is added to yield a molding powder upon drying, which when heated in a mold gives a water-white (transparent) molding unless previously coloured by pigment.

The filler confers considerable strength, so that thin sections such as in cups and tumblers can be molded. Very large quantities of urea-formaldehyde resin are used in kitchen and bathroom hardware details, and electric ap­pliance housings and fittings.

Melamine behaves in the same way as urea, but the prod­uct is more moisture resistant, harder and stronger, lead­ing to wide use for plates and food containers. Melamine moldings are glossy and harder than any other plastic and retain a dust-free surface. Solutions of the thermoplastic forms of urea-formaldehyde resins are widely used as bonding agents for plywood and wood-fibre products.

Alkyds

Alkyds are polyesters, generally of phthalic acid (with two acid groups) and glycerol, a triol — i. e., an alcohol with three hydroxyl groups. The solid resins are molded at high speed under low pressure, cured quickly, and are used where insulating properties, strength, and dimen­sional stability over a wide range of voltage, frequency, temperature, and humidity are required, as in vacuum-tube bases and automotive ignition parts and with glass-fibre reinforcement for switch gear and housings for portable tools.

Polyesters of unsaturated alcohols

The resins known as DAP and DAIP, are crossliked allyl esters of phthalic and isophthalic acid, respectively. They are notable for maintaining rigidity and excellent electrical properties at temperatures up to 230 С, prорerties also manifested by allylic resin-impregnated glass cloth, used in aircraft and missile parts. Other advan­tages are good storage life and absence of gas evolution during polymerization. The resin allyl diglycol carbon­ate, optically clear and colourless, is used for making cast objects; fully cured castings are more heat and abrasion resistant than other cast resins.

Epoxy resins

Epoxy resins have outstanding mechanical and elec­trical properties, dimensional stability, resistance to heat and chemicals, and adhesion to other materials. They are used for casting, encapsulation, protective coat­ings, and adhesives, and for reinforced moldings and laminates of the highest quality. Popular adhesives (epoxy glues) contain the resin components and the cur­ing agent, usually an amine or an anhydride, in separate packages. The two are mixed just before use.

Polyurethanes

Formed by the reaction between diisocyanates and polyols (multihydroxy compounds), polyurethanes are among the most versatile of plastics, ranging from rigid to elastic forms. Their major use is for foams, with prop­erties varying from good flexibility to high rigidity. Thermoplastic polyurethanes that can be extruded as sheet and film of extreme toughness can also be made.

Polyesters of unsaturated acids

Certain esters can be polymerized to resin and are used on a very large scale in glass-fibre-reinforced plastics.

Unsaturated acid (usually maleic acid in the form of its anhydride) is first polymerized to a relatively short polymer chain by condensation with a dihydric alcohol such as propylene glycol, the chain length being deter­mined by the relative quantities of the two ingredients The resulting condensation polymer is then diluted with a monomer such as styrene and an initiator for addition polymerization added. This mixture is quite stable at room temperature over a long period. Frequently, a silicone compound is added to promote adhesion to glass fi­bres, and wax to protect the surface from oxygen inhibi­tion of polymerization. Glass-fibre materials are impreg­nated with the syrup and polymerization is brought about by raising the temperature. Alternatively, the polymeri­zation can be carried out at room temperature by addition of a polymerization accelerator to the syrup immediately before impregnation. After an induction period, which can be controlled, polymerization takes place, with rapid in­crease in temperature, to give a glass-fibre-reinforced cross-linked polymer, which is effectively a thermoset type of plastic and very resistant to heat. The properties of the resin are frequently varied by replacing part of the unsaturated maleic anhydride by anhydrides of satu­rated acids.

Silicones

Silicon, unlike carbon, does not form double bonds or long silicon chains. It does, however, form long chains with oxygen such as in siloxanes with hydrocarbon groups attached to the silicon; these result in a wide range of oils, greases, and rubbers.

Produced through a series of reactions involving re­placement of certain atoms in the chain, silicon resins, or silicones, can be used for high- and low-pressure lami­nation, with glass-fibre reinforcement and with mineral or short glass-fibre fillers, or for molding powders. The outstanding characteristic of these products is high di­electric strength (that is, they are good insulators at high voltages) with low dissipation over a wide temperature and humidity range. Silicones are not distorted by heat up to 400 С. They are also physiologically inert and there­fore valuable for prostheses (artificial body parts).

 


5. INDUSTRIAL PLASTICS:

 

RIGID AND FLEXIBLE FOAMS

Rigid polyurethane foams in sandwich forms have wide applications as building components. They are also the best insulants known today and so have wide appli­cation in refrigeration and in buildings, where they are applied in fitted slab form or are foamed into cavities at the building site. They can also be applied by spraying about six millimetres thickness with each pass of the spray gun. The ability to spray a foaming mixture through a single nozzle is a great advantage in applica­tion.

A very important use of rigid foam is for furniture parts to reproduce wood structures; these can be injec­tion molded. Polyurethane foam can be screwed and nailed with a retention about equal to white pine lum­ber.

A major advance in the manufacture of sandwich structures is a new method of injection molding, in which a large machine is used to produce moldings up to 1.2 metres square. Moldings of great strength and any de­sired surface are obtained.

Flexible foams

Flexible foams, usually polyurethane, are made in slab form up to 2.4 metres in width and as much as 1.5metres high; these are then cut to required shapes or sizes or are molded. The molded foams may be hot molded.

This involves filling heated aluminum castings and gives a product having high resistance to compres­sion, as for automobile seats; or they may be cold molded, a process used particularly for semi-flexible foams with high load-bearing properties. Used almost exclusively by the automobile industry for crash pads, armrests, and dashboard covers, the process involves machine mixing the ingredients and pouring them into aluminum molds lined with vinyl or acrylo-nitrile-butadiene-styrene skins, which become the cover material for the part.

Polystyrene foams are made in a wide range of densi­ties, from expandable beads, either by extrusion through slot-shaped openings to 40 times the original volume to form boards directly or by foaming in steam chests to form large billets. Using small beads in stainless steel molds, cups can be molded with thin sections.

Thin sheet for packaging can also be made by the tube extrusion technique. Though packaging is a major use for forms made in closed molds, the largest use is for building panels; they can be plastered directly.

Acrylonitrile-butadiene-styrene can be expanded from pellets and is particularly suitable for wood-grain effects and for the production of heavy sections.

Expanded vinyls can be made from plastisols for flooring or textile linings by calendering with a blow­ing agent and laminating to a fabric base, and by injec­tion molding for insulation and such articles as shoe soles. An improved material is now obtained from cross-linked polyvinyl chloride and competes with polyester in glass reinforced plastic.

 


6. BASIC PRINCIPLES OF WELDING

A weld can be defined as a coalescence of metals pro­duced by heating to a suitable temperature with or with­out the application of pressure, and with or without the use of a filler material.

In fusion welding a heat source generates sufficient heat to create and maintain a molten pool of metal of the required size. The heat may be supplied by electricity or by a gas flame. Electric resistance welding can be consid­ered fusion welding because some molten metal is formed.

Solid-phase processes produce welds without melting the base material and without the addition of a filler metal. Pressure is always employed, and generally some heat is provided. Frictional heat is developed in ultra­sonic and friction joining, and furnace heating is usu­ally employed in diffusion bonding.

The electric arc used in welding is a high-current, low-voltage discharge generally in the range 10-2,000 am­peres at 10-50 volts. An arc column is complex but, broadly speaking, consists of a cathode that emits elec­trons, a gas plasma for current conduction, and an anode region that becomes comparatively hotter than the cath­ode due to electron bombardment. Therefore, the elec­trode, if consumable, is made positive and, if non-consum­able, is made negative. A direct current (dc) arc is usually used, but alternating current (ac) arcs can be employed.

Total energy input in all welding processes exceeds that which is required to produce a joint, because not all the heat generated can be effectively utilized. Efficiencies vary from 60 to 90 percent, depending on the process; some special processes deviate widely from this figure. Heat is lost by conduction through the base metal and by radiation to the surroundings.

Most metals, when heated, react with the atmosphere or other nearby metals. These reactions can be extremely detrimental to the properties of a welded joint. Most metals, for example, rapidly oxidise when molten. A layer of oxide can prevent proper bonding of the metal. Molten-metal droplets coated with oxide become en­trapped in the weld and make the joint brittle. Some valu­able materials added for specific properties react so quickly on exposure to the air that the metal deposited does not have the same composition as it had initially. These problems have led to the use of fluxes and inert atmospheres.

In fusion welding the flux has a protective role in fa­cilitating a controlled reaction of the metal and then pre­venting oxidation by forming a blanket over the molten material. Fluxes can be active and help in the process or inactive and simply protect the surfaces during joining.

Inert atmospheres play a protective role similar to that of fluxes. In gas-shielded metal-arc and gas-shielded tungsten-arc welding an inert gas—usually argon—flows from an tube surrounding the torch in a continuous stream, displacing the air from around the arc. The gas does not chemically react with the metal but simply pro­tects it from contact with the oxygen in the air.

The metallurgy of metal joining is important to the functional capabilities of the joint. The arc weld illus­trates all the basic features of a joint. Three zones result from the passage of a welding arc: (1) the weld metal, or fusion zone, (2) the heat-affected zone, and (3) the unaf­fected zone. The weld metal is that portion of the joint that has been melted during welding. The heat-affected zone is a region adjacent to the weld metal that has not been welded but has undergone a change in microstructure or mechanical properties due to the heat of weld­ing. The unaffected material is that which was not heated sufficiently to alter its properties.

Weld-metal composition and the conditions under which it freezes (solidifies) significantly affect the abil­ity of the joint to meet service requirements. In arc weld­ing, the weld metal comprises filler material plus the base metal that has melted. After the arc passes, rapid cool­ing of the weld metal occurs. A one-pass weld has a cast structure with columnar grains extending from the edge of the molten pool to the centre of the weld. In a multipass weld, this cast structure maybe modified, depending on the particular metal that is being welded.

The base metal adjacent to the weld, or the heat-af­fected zone, is subjected to a range of temperature cy­cles, and its change in structure is directly related to the peak temperature at any given point, the time of expo­sure, and the cooling rates. The types of base metal are too numerous to discuss here, but they can be grouped in three classes: (1) materials unaffected by welding heat, (2) materials hardened by structural change, (3) materi­als hardened by precipitation processes.

Welding produces stresses in materials. These forces are induced by contraction of the weld metal and by ex­pansion and then contraction of the heat-affected zone. The unheated metal imposes a restraint on the above, and as contraction predominates, the weld metal cannot con­tract freely, and a stress is built up in the joint. This is generally known as residual stress, and for some critical applications must be removed by heat treatment of the whole fabrication. Residual stress is unavoidable in all welded structures, and if it is not controlled bowing or distortion of the weldment will take place.

Arc welding

Shielded metal-arc welding accounts for the largest total volume of welding today. In this process an electric arc is struck between the metallic electrode and the workpiece. Tiny globules of molten metal are transferred from the metal electrode to the weld joint. Arc welding can be done with either alternating or direct current. A holder or clamping device with an insulated handle is used to conduct the welding current to the electrode. A return circuit to the power source is made by means of a clamp to the workpiece.

Gas-shielded arc welding, in which the arc is shielded from the air by an inert gas such as argon or helium, has become increasingly important because it can deposit more material at a higher efficiency and can be readily automated. The tungsten electrode version finds its ma­jor applications in highly alloyed sheet materials. Either direct or alternating current is used, and filler metal is added either hot or cold into the arc. Consumable elec­trode gas-metal arc welding with a carbon dioxide shield­ing gas is widely used for steel welding. Metal transfer is rapid, and the gas protection ensures a tough weld.

Submerged arc welding is similar to the above except that the gas shield is replaced with a granulated mineral material as a flux.

Weldability of metals

Carbon and low-alloy steels are the most widely used materials in welded construction. Carbon content largely determines the weldability of carbon steels. Low-alloy steels are generally regarded as those having a total al­loying content of less than 6 percent. There are many grades of steel available, and their relative weldability varies.

Aluminum and its alloys are also generally weldable. A very thin oxide film on aluminum tends to prevent good metal flow, however, and suitable fluxes are used for gas welding. Fusion welding is more effective with alternat­ing current when using the gas-tungsten arc process to enable the oxide to be removed by the arc action.

Copper and its alloys are weldable, but the high ther­mal conductivity of copper makes welding difficult. Me­tals such as zirconium, niobium, molybdenum, tantalum, and tungsten are usually welded by the gas-tungsten arc process. Nickel is the most compatible material for join­ing, is weldable to itself, and is extensively used in dis­similar metal welding of steels, stainless steels and cop­per alloys.

 


7. GEAR

Gear is a toothed wheel or cylinder used to transmit rotary or reciprocating motion from one part of a ma­chine to another. Two or more gears, transmitting mo­tion from one shaft to another, constitute a gear train. At one time various mechanisms were collectively called gearing. Now, however, gearing is used only to describe systems of wheels or cylinders with meshing (постоянное зацепление) teeth. Gearing is chiefly used to transmit rotating motion, but can, with suitably designed gears and flat-toothed sectors, be employed to transform re­ciprocating motion into rotating motion, and vice versa.

Simple Gears

The simplest gear is the spur (зубчатая) gear, a wheel with teeth cut across its edge parallel to the axis. Spur gears transmit rotating motion between two shafts or other parts with parallel axes. In simple spur gearing, the driven shaft revolves in the opposite direction to the driving shaft. If rotation in the same direction is desired, an idler gear (паразитная) is placed between the driving gear and the driven gear. The idler revolves in the oppo­site direction to the driving gear and therefore turns the driven gear in the same direction as the driving gear. In any form of gearing the speed of the driven shaft depends on the number of teeth in each gear. A gear with 10 teeth driving a gear with 20 teeth will revolve twice as fast as the gear it is driving, and a 20-tooth gear driving a 10-tooth gear will revolve at half the speed. By using a train of several gears, the ratio of driving to driven speed may be varied within wide limits.

Internal, or annular, gears are variations of the spur gear in which the teeth are cut on the inside of a ring or flanged wheel rather than on the outside. Internal gears usually drive or are driven by a pinion, a small gear with few teeth. A rack, a flat, toothed bar that moves in a straight line, operates like a gear wheel with an infinite radius and can be used to transform the rotation of a pin­ion to reciprocating motion, or vice versa.

Bevel gears (конические передачи) are employed to transmit rotation between shafts that do not have paral­lel axes. These gears have cone-shaped bodies and straight teeth. When the angle between the rotating shafts is 90°, the bevel gears used are called mitre gears.

Helical Gears

These gears have teeth that are not parallel to the axis of the shaft but are spiraled around the shaft in the form of a helix. Such gears are suitable for heavy loads because the gear teeth come together at an acute angle rather than at 90° as in spur gearing. Simple helical gearing has the disadvantage of producing a thrust that tends to move the gears along their respective shafts. This thrust can be avoided by using double helical, or herringbone, gears, which have V-shaped teeth composed of half a right-handed helical tooth and half a left-handed helical tooth. Hypoid gears are helical bevel gears employed when the axes of the two shafts are perpendicular but do not in­tersect. One of the most common uses of hypoid gearing is to connect the drive shaft and the rear axle in motor cars. Helical gearing used to transmit rotation between shafts that are not parallel is often incorrectly called spiral gearing.

Another variation of helical gearing is provided by the worm gear, also called the screw gear. A worm gear is a long, thin cylinder that has one or more continuous heli­cal teeth that mesh with a helical gear. Worm gears dif­fer from helical gears in that the teeth of the worm slide across the teeth of the driven gear instead of exerting a direct rolling pressure. Worm gears are used chiefly to transmit rotation, with a large reduction in speed, from one shaft to another at a 90° angle.


BEARINGS

Bearing is a mechanical device for decreasing friction in a machine in which a moving part bears—that is, slides or rolls on another part. Usually in a bearing the support must allow the moving part one type of motion, for ex­ample, rotation, while preventing it from moving in any other way, for example, sidewise. The commonest bear­ings are found at the rigid supports of rotating shafts where friction is the greatest.

Bearings were invented early in history; when the wheel was invented, it was mounted on an axle, and where wheel and axle touched was a bearing. Such early bear­ings had surfaces of wood or leather lubricated with ani­mal fat.

Modern bearings have been arbitrarily designated as friction bearings and antifriction bearings. The first comprises sleeve or journal bearings; the second, ball and roller bearings. Neither type of bearing is completely frictionless, and both are highly efficient in reducing friction. A large, modern aircraft engine, for example, has more than 100 bearings, including both types; yet the total power consumed in overcoming bearing friction is less than one per cent of the total power output of the engine.

Friction bearings (скольжения) of the sleeve or jour­nal type are simpler than antifriction bearings in construc­tion but more complex in theory and operation. The shaft supported by the bearing is called the journal, and the outer portion, the sleeve. If journal and sleeve are both made of steel, the bearing surfaces, even if well lubricated, may grab or pick up, that is, rip, small pieces of metal from each other. The sleeves of most bearings therefore are lined with brass, bronze, or Babbitt metal. Sleeve bearings are generally pressure-lubricated through a hole in the journal or from the housing that contains the bear­ing. The sleeve is often grooved to distribute the oil evenly over the bearing surface.

Typical clearance (difference between the diameters of journal and sleeve) is nominally 0.0025 cm for every 2.54 cm of journal diameter. When the journal is rotat­ing, it may be about 0.0000001 cm from the sleeve at the side with the greatest load. The journal is thus supported on an extremely thin film of oil, and the two parts have no actual contact. As the rotational speed increases, other variables remaining constant, the oil film becomes thicker, so that the friction increases in less than direct proportion to the speed. Conversely, at lower speeds the oil film is thinner if other factors are unchanged. At ex­tremely low speeds, however, the film may rupture and the two pieces come into contact. Therefore, friction is high when the machine is started in motion, and the bear­ing may fail if high stresses are put on it during start­ing. Ball bearings, on the other hand, have low starting friction.

Jewel bearings are used to mount very little shafts such as those found in fine watches. They are friction-type bearings in which the ends of the shafts are mounted in extremely hard substances. The bearing is lubricated with a microscopic drop of fine oil.

In a ball bearing, a number of balls rotate freely be­tween an inner ring, which is rigidly fixed to a rotating shaft, and an outer ring, which is rigidly fixed to a sup­port. Both balls and rings are made of hardened alloy steel, usually finished to extremely fine tolerances. The balls are generally held in position by a cage or separator that keeps them evenly spaced and prevents them from rubbing against each other. The bearing is lubricated with grease or oil.

A roller bearing is similar to a ball bearing, except that small steel cylinders, or rollers, are substituted for the balls. A needle bearing is a roller bearing in which the rollers are extremely long and thin. An ordinary roller bearing may have 20 rollers — each twice as long as it is wide — whereas a needle bearing may have 100 needles, each 10 times as long as it is wide. Needle bearings are particularly useful when space is limited.





Читайте также:
Книжный и разговорный стили речи, их краткая характеристика: В русском языке существует пять основных...
Социальные науки, их классификация: Общество настолько сложный объект, что...
Роль химии в жизни человека: Химия как компонент культуры наполняет содержанием ряд фундаментальных представлений о...
Развитие понятия о числе: В программе математики школьного курса теория чисел вводится на примерах...

Рекомендуемые страницы:



Вам нужно быстро и легко написать вашу работу? Тогда вам сюда...

Поиск по сайту

©2015-2021 poisk-ru.ru
Все права принадлежать их авторам. Данный сайт не претендует на авторства, а предоставляет бесплатное использование.
Дата создания страницы: 2017-03-31 Нарушение авторских прав и Нарушение персональных данных


Поиск по сайту:

Мы поможем в написании ваших работ! Мы поможем в написании ваших работ! Мы поможем в написании ваших работ!
Обратная связь
0.033 с.