FI77900B - FOERFARANDE OCH ANORDNING FOER ELBELAEGGNING AV FIBER. - Google Patents

Description

1 77900

The present invention relates to a method according to the preamble of claim i and an apparatus according to the preamble of claim 25 for electroplating fibers with a metal.

Fibers consisting of non-metals and semi-metals such as carbon, boron, silicon carbide, polyester, nylon, aramid, cotton, rayon, and the like, in the form of monofilaments, yarns, ropes, mats, fabrics, and staple fibers, are known to be useful in reinforcing metals and organic polymeric materials. For products comprising metals or plastics reinforced with such fibers, there is widespread use in replacing heavier components made from lower strength conventional materials such as aluminum, steel, titanium, vinyl polymers, aircraft, nylons, polyones, polyesters. , office equipment, sporting goods-20 sa and many other areas.

A common problem with the use of such filaments, and also glass, asbestos, and the like, is the apparent lack of skill in transferring the properties of high strength filaments to the material to which final and close contact is to be made. In essence, even if a high-strength thread is used, the threads are merely mechanically retained and the resulting composite breaks and breaks with annoyingly low applied forces.

The problems have been partially overcome by depositing a metal layer or layers on the surface of the individual strands before they are joined to the bonding material, for example metal or plastic. Metal deposition is accomplished by vacuum deposition, e.g., on the surface of nickel fibers, as described in U.S. Patent 4,132,828, and electroless deposition on chemical baths, e.g., nickel on graphite filaments, as described in U.S. Patent 3,894,677, and electroprecipitation, e.g. electroplating nickel on the surface of carbon fibers as described in Sara, U.S. Pat. No. 3,622,283 and Sara, U.S. Pat. No. 3,807,996.

When metal-coated filaments according to such procedures are twisted or sharply bent, a very substantial amount of metal slips off or falls off as a powder. When such metal-coated filaments are used to reinforce either metals or polymers, the ability to resist compression and tensile stress is much less than might be expected from the alloy rule, and this strongly suggests that the failure of effective reinforcement is due to the bond between the filament and the metal. is bad.

It has now been found that if electroplating is selected and a voltage amount greater than that required to simply dissociate (reduce) the electrically precipitable metal ion to the surface of the filament is selected and used, an excellent bond is obtained between the filament and the metal layer. The strength is such that when the metal-coated thread is bent, the coating may break but will not peel off. In addition, continuous lengths of such metal-coated filaments can be knotted and twisted without a substantial portion of the metal being lost as flakes or powder. The high voltage is believed to be important in obtaining or facilitating the uniform formation of crystalline embryos on the surface of the filament of the electroprecipitating metal, and in overcoming the barrier or barrier effect of the materials absorbed on the surface of the filament.

Although a certain amount of electricity is required to electrically dop the metal on the surface of the strand, an increase in voltage to increase the amperes can cause the strands to burn, which would interrupt the continuous process. The aforementioned 35 Sara Patent No. 3,807,966 uses a continuous process for nickel plating of granular wire, but uses a plating current of only 2.5 amps and long deposition times, for example 14 minutes, and therefore low and conventional voltages. In another continuous process described in GB Patent No. 1,272,777, the individual fibers in a fiber bundle are electrically coated without burning them by passing the bundle through an electrolyte jet carrying the coating material, the bundle being held at a negative potential relative to the electrolyte. on the surface of graphite, with the potential between the anode and the fibers being the usual 3 volts.

The present invention provides an efficient device to facilitate increasing the potential between the anode and the cathode formed by the continuous strand, as a key aspect of this method is to increase the voltage to obtain excellent metal-coated fibers. In addition, because it allows additional electrical energy to be introduced into the system without the filaments burning, the settling time is shortened and the manufacturing speeds increase very much above the previously known speeds. As will be apparent from the detailed description that follows, new means are used to provide high-voltage coating, strategic cooling, efficient electrolyte-fiber contact, and high-speed fiber transport in 25 different combinations, all leading to improved metal-coated fiber fabrication speed and quality. Such filaments are essentially useful, for example, when combined with thermoplastic and thermosetting press compounds for aircraft lightning protection, EMI / RFI protection, and other applications that require electrical / thermal conductivity. They are also useful in high surface area electrodes in electrolytic cells. Composites in which such strands are oriented substantially parallel dispersed in a metal matrix, for example nickel-plated graphite in a lead or zinc 77900 4 matrix, are characterized by lightness and excellent resistance to compression and tensile stress. The device of the present invention can also be used to improve the fabrication speed and product quality when electrically coating non-conductive continuous filaments, e.g. polyaramides or cotton, etc., if a tacky electrically conductive inner layer, e.g. chemically, is first deposited on the non-conductive filament.

The basic object of the present invention is to provide fibers formed of a conductive semi-metallic core with a metallic coating.

Another object of the present invention is to provide a method in which the electroplating of fibers is achieved under high voltage electroplating conditions.

It is a further object of the present invention to provide a method and apparatus that efficiently and rapidly coat fibers with metal coatings and facilitate rinsing and assembly of the finished product.

Still another object of the present invention is to provide fibers uniformly coated around their diameter to such an extent that the deviation of the coating thickness is less than 10%.

It is also an object of the present invention to coat all the fibers in the rope with the same material thickness, within ten to 25 percent, regardless of whether the rope thickness is small or large, that is, 3K-12 x 12K.

It is a further object of the present invention to provide a method by which metallic filaments, in particular metal-coated filaments, can be provided with properties which help to facilitate mixing with organic plastic materials and which properties which are desirable or necessary for weaving metal-coated metals can be obtained. fibers into fabric or ma-like articles.

It is a further object of the invention to provide 5,77900 metallic filaments with lubricity.

Yet another object of the invention is to provide metal-coated high strength fibers with a minimum number of random fibrils extending outwardly from the base fiber.

Yet another object of the invention is to provide metallized filaments having a metal oxide surface layer.

It is a further object of the invention to provide composites, for example laminates, comprising metallized filaments having a surface treated with a finishing agent and / or oxidation and an organic polymer matrix.

It has been found that these and other objects are achieved by the method according to claim 1 and the device according to claim 25.

According to the present invention, there is provided an apparatus in which a plurality of fibers can be simultaneously effectively coated on a metal surface and subsequently cleaned and twisted for use in a variety of end products.

The device is usually equipped with a release section adapted to supply a large amount of fibers to the electrolytic coating bath. The pretreatment process involves trisodium phosphate purification, rinsing, and acid-25 washing. In coating applications where non-conductive fibers are coated, the pretreatment methods may also comprise roughening or grinding the fibers followed by chemical deposition of a thin metallic interlayer. Thereafter, the net coating is performed in a continuous process by passing pure fibers through an electrolyte, where the coating of the fibers is performed under high voltage conditions. Equipped with devices for cooling the fibers as they pass away from the contact roll associated with the electrolyte reservoir and the electrolyte bath. Preferred devices, in essence, include 6,779,000 electrolyte recycling at strategic points over contact rollers and fiber. The process also takes into account a series of separate electrolyte tanks connected to separate rectifiers to facilitate the coating of the alternating current 5. The current varies as a function of the resistance developed by the coating of the surface of the fibers.

After the coating is completed, the coated fibers are rinsed with water and treated with steam and then dried.

Tight bonding, high voltage metal coated fibers made by the apparatus and method of this invention are very useful as reinforcements to provide improved fiber-resin matrix composites. In these final applications, it is still desirable to finish the surface of the metal-coated fibers so that they are easier to knit or weave into carpet or fabrics, and to provide better compatibility with the matrix resins or metals they reinforce.

According to this aspect of the invention, the post-treatment finishing process of the present invention is characterized by feeding metallic filaments to a medium comprising a coupling and finishing agent, e.g. aminosilane, alone or in combination with a medium comprising a filler and polymer finishing agent, e.g. polyvinyl acetate. Further treatment of the material is also possible by passing the material through dispersants, fluxes and / or an external lubricant and finishing agent, for example a polyethylene emulsion, in combination with or after removal from the filler and polymer finishing bath. This process as a whole is appropriately considered a finishing touch. During the intermediate step or after the finishing steps have been completed, the fibers can be heated to dry and place the finishing material on the surface of the fibers.

It is also a feature of the present invention to provide a method for oxidizing the surface of metal filaments under controlled conditions, alone or in combination with further finishing.

5 As a result of the high-voltage electroplating process, the continuous line is equipped with devices for synchronizing each of the process steps with each other. The high voltage environment also comprises a specially designed commutation system for contact rollers with fingers of different lengths, of which a specially designed anode arrangement comprising an anode basket is partially coated with an insulator to protect it from the electrolysis bath.

Flushing tanks and electrolyte tanks are specially designed for the treatment of the electrolyte surface and for the minimal accumulation of waste flushing liquid.

Special rollers developed for use in further relaxation aid in the efficiency of the method.

The invention will be more readily understood when examined in connection with the following figures, in which Figure 1 is a block diagram of the overall process of the subject continuous electrolysis coating process with the exception of the loosening section, Figure 2 is an elevational view of is a plan view of the loosening part of Fig. 2, Fig. 4 is a vertical cross-sectional view of the loosening roller part, Fig. 5 is a section along line 5-5 of Fig. 4, Fig. 6 is an isometric view of the wetting and tension rollers between loosening and electrolysis bath, Fig. 7 is a vertical section Fig. 8 is an elevational view of one electrolysis tank, Fig. 9 is a plan view of the reservoir of Fig. 3, 8 77900 Fig. 1Q is a vertical sectional view taken along line 10-10 of Fig. 0, Fig. 11 is an isometric view of a switching finger, Fig. 12 is an isometric view of one contact roller Fig. 13 is an elevational view of an electrolyte reservoir illustrating the anode basket; Fig. 14 is a plan view of devices for supplying electrolyte to the fibers extending into contact with the apparatus which supplies the coolant to the fibers and the flow-carrying medium from the contact roll to the bath; from roll to electrolysis bath, Fig. 15 is a detailed plan view of the spray nozzles of Fig. 12, Fig. 16 is a view of the electrolyte coolant conductor and contact roll, Fig. 17 is a vertical sectional view of the contact roll of the process assembly, Fig. 13 is a detail of the roll end of Fig. 17, Fig. from the opposite end, Fig. 20 is a partial exposed cross-sectional view of the contact holder for the anode basket, Fig. 21 is an isometric view of the anode basket of the invention, Fig. 22 is a view of the electrical system of the present invention, Fig. 23 is a vertical sectional view of the flushing tanks and Fig. 24 is a cross-sectional view of the wash three-branch of the invention, Fig. 25 is a view taken along line 25-25 of the wash three branch of Fig. 24, Fig. 26 is a view taken along line 26-26 of the wash branch of Fig. 24, Fig. 27 is a view of the mechanism, Fig. 28 is a plan view taken along line 28-28 in the section of Fig. 27, Fig. 29 is a vertical side view of the roller assembly in the drying section of the system, Fig. 30 is a cross-section of the guide roller through line 30-30 of Fig. 29, Fig. 31 Fig. 32 is a longitudinal cross-sectional view of a metal-coated rough-surfaced filament according to the present invention; Fig. 33 is a fragmentary view of a portion of Fig. 32; obtained using the present invention, Fig. 35 is k Fig. 36 is a cross-sectional view of a metal-coated fiber made by the improved method of the present invention; Fig. 36a is a longitudinal cross-sectional view of a metal-coated fiber made by the improved method of the present invention; kek-25 according to the improved method of the invention, Figs. 37 and 37a are cross-sectional and longitudinal cross-sectional views, respectively, of a core fiber having a coating not in accordance with the present invention, showing a non-uniform coating resulting from organic compound 30 impurity; 38 is an enlarged photograph of a metal-coated fiber made in accordance with the present invention having a uniform coating because the core fiber was clean of dirt-35 wind caused by organic compounds; 1Q 7790 0 Fig. 39 is an enlarged photograph of a fiber of a non-k according to the invention, and which does not have a uniform coating because the core fiber was soiled due to adsorbed organic compounds, and Fig. 40 is a vertical sectional view of a method and apparatus used for finishing and / or surface oxidation of metal strands, e.g., metal-coated high strength fibers.

The method and apparatus of the present invention are intended to provide efficient and complete means for coating metal with non-metallic and semi-metallic fibers.

The method of the present invention depends on the use of very high voltages and currents to provide a satisfactory coating. As a result of high voltage and current, a device has been developed that can produce large volumes of coated material under high voltage conditions.

A method and apparatus according to the present invention, which is particularly suitable for carrying out the method according to the invention in practice, is described in a preferred embodiment, in which the specified fiber to be coated is carbon or graphite fiber and the coating metal is nickel. However, the apparatus and method of the present invention are suitable for virtually the entire spectrum of metal coating of non-metallic and semi-metallic fibers.

The method as a whole and a picture of the device with the exception of the loosening part are generally seen in Figure 1.

The operative method essentially comprises a loosening part for dividing the multiple fibers in parallel, tension rollers 6, and a pretreatment part 8, a coating device 10, a rinsing station 12, a drying part 14 and receiving coils 16.

More specifically, the pretreatment section 8, shown generally in Figure 1, comprises a trisodium phosphate purifier 77900 distillation section 26 and an associated wash triangle 28, a rinse portion 30 and associated wash triangles 32 and 32A, a hydrochloric acid portion 34 and an associated triple branch 36, and a rinse 38 and associated wash triangles 40 and 5 40A, all illustrated in Figure 7. The coating device 10 consists of a plurality of electrolyte tanks arranged in series, shown illuminatingly in Figure 1 as tanks 18, 20, 22 and 24, each loaded with current by a separate rectifier. which are better seen in Figures 8 and 22. The flushing section 12, generally seen in Figure 1, consists of tank and three-branch sections similar to the pretreatment device. An arrangement consisting of cascade tanks 42 and triangular arms 44, 44A and 44B circulates the rinsing solution consisting of water and electrolyte 15 over the fibers 2. Pure water is then passed over the fibers 2 in a rinsing section 46 provided with tanks and rinsing triangles 48 and 48A. more particularly in Figure 26. The rinsed fiber 2 is passed through a section 50 where it is air blown in a lower section 20 in a section 53 and then steam treated in a section 55 to produce an oxide surface on the metal surface. The process is terminated by passing the metal-coated fiber 2 through a drying unit 14 and winding the finished fibers onto the take-up reels 17 in the winding section 16.

As can be seen in general in Figure 1, the apparatus is provided with means for rapidly conveying the fibers 2 through the system without scraping the fibers 2.

The combination of strategically placed guide rollers 51, tension rollers 6, force determining rollers 3Q in the drying section 14 and the synchronous drive assembly shown in Figure 27 quickly moves the fibers 2 through the apparatus so that the fibers 2 do not wear out.

The operation begins with the loosening part 4 shown in Figures 2 and 3. Functionally, the fibers 2 from the Höllen-35 section 4 are fed over the guide roller 5 via tension rollers 6 to the pretreatment section 8.

12 77 90 0

As best seen in Figures 2 and 3, the loosening part 4 consists of a frame 52 in which the loosening rollers 54 are mounted. The structure of the rollers 54 is better seen in Figures 4 and 5 and will be described more specifically in connection with Figures 4 5 and 5. The loosening rollers 54 are mounted to the frame 52 by rail 56 and rail 58. The rollers 54 by rail 56 are arranged to loosen the fibers 2 in the electroplating system, while rail 58 is an auxiliary rail suitable for securing spare rollers 54 available for 1Q backup operation. The rail 60 secures a guide roller 62 over which the fibers 2 from the loosening rollers 54 pass to reach the tension rollers 6.

As best seen in Figure 2, the fibers 2 extend from the respective rollers 54 over a single guide roller 15 62 associated with the particular roller 54, the general guide roller 5 and the tension roller section 6. The guide rods 59 guide the fibers 2 from the loosening rollers 54 to their associated guide rollers 62.

As can be seen in Figure 3, the guide rollers 62 are placed in a row 2Q next to each other to avoid a collision between the fibers 2 when a large number of fibers 2 are fed into the system simultaneously for processing and coating.

The structure of the loosening rollers 54 is best seen in Figures 4 and 5. The loosening rollers 54 consist essentially of a centrally located rod 66 having end roller bearings 68 and 70 and arranged to fit into a crimping frame 64 formed by yarns 72. Practice has taught that four the resilient yarn 72 arranged at 90 degrees from each other may form a frame 64 suitable for attaching most commercial fiber spools. The bearing 68 is arranged to support either track 56 or track 58 in the Höllen section 4.

The rod 66 is provided with a threaded end 76, 13 77900 which passes through an opening in the rails 56 or 58. A conventional nut is used (not shown) to secure the Höllen roll 54, which is thus freely mounted with a free end bearing 70 having a tensile strength of tan-5 by 66. Thus, if the loose roll frame wires are compressed, bearing 70 can move transversely to the rod 66. the frame yarns 72 are provided with conical ends 74. As a result of the conicity of the frame yarns 72 and the transversely movable plate 10, the compressible frame 64 can adapt to accommodate fiber sides of different diameters. The loosening section 4 feeds the fibers 2 over the guide roller 5 to the wetting roller 80 and then to the tensioning rollers 6. The wetting barrel 84 is provided with water which wets the fibers 2 and 15 possibly during a suitable and more efficient cleaning and rinsing of the fibers 2. The tension rollers 6 shown in Figure 1 are seen in more detail in Figure 6.

The tension rollers 6 comprise an assembly of five rollers 90, all of which are driven by a single continuous chain 87 by a conventional source, such as a speed controlled motor 92. Each roller 90 is mounted on a shaft 89 which also secures a fixed gear around which the chain 87 passes. -25 kee. The idler rollers 97 are also arranged to engage the chain 87. A gear 93 extending from the shaft 95 of the speed controlled motor 92 drives a continuous chain 87 via a chain 101 and a gear 1Q3 attached to the shaft 89 of the roller 90. It is necessary that the stress be applied to the fibers at point 2, which is aligned upstream of the first coating contact roll. The coating contact roll and the fibers 2 must be in tight contact to facilitate the operation at the high voltage and high current necessary for the method. By means of the Tiu-35 contact between the fibers 2 and the contact rollers 14,77900, a low resistance is obtained, thus the high current flowing through the system circuit does not overload the fibers 2, causing the fibers to be destroyed. As a result, the tension roller assembly 6 is placed upstream of the electric overflow tanks 18, 2Q, 22, 24 (Fig. 1) to provide this tension. On the other hand, the fibers should be subjected to as little resistance as possible. Inherent in the fibers 2 tends to separate on the surface and assemble the fibers. The variable drive motor 92 is coupled to all five rollers 90, 10 to provide a variable speed to the rollers at a speed equal to or less than the speed of the fibers 2. At carefully controlled speeds, the necessary tension is provided so that no fiber entanglement occurs on the fibers. The apparatus and method are designed for an A-15 tension roller assembly 6 in which the tension rollers 90 travel at a lower speed than the fibers 2. The tension in the fibers 2 is maintained by changing the speed of the tension roller 90 in response to visual determination of the tension.

The fibers to be coated according to the new apparatus and method of the present invention are first purified in a pretreatment section 3. The pretreatment provides an improvement comprising providing core fibers whose surfaces are substantially free of adsorbed organic compounds that interfere with the electrical precipitation of the metal. A surface substantially free of organic adsorbed compounds can be obtained by removing them from the core fiber, for example, by solvent purification, chemical purification, high temperature purification, and the like.

The term "substantially free" as used herein and in the appended claims means a very low amount of adsorbed organic compounds, that is, an amount that does not interfere with the coating and promotes uneven coating. It is very difficult to remove or avoid all traces of 15 7 7900 kia, but usually an amount extending to about 5% of the short length area can be coated and allowed, without serious disadvantage.

In one pre-purification treatment, a substantially free surface of adsorbed organic compounds is obtained by removing substantially all such compounds by contacting the core fibers with solvents suitable for such compounds. A useful solvent is 1,1,1-trichloroethane. This can be used in 10 conventional degreasers. Due to the high purity requirements of the purified fiber, the solvent must be changed or cleaned frequently.

In a preferred embodiment illustrated in Figure 1, the adsorbed organic compound-free surface is obtained by removing substantially all such compounds by contacting the fibers with an aqueous solution of an inorganic detergent, preferably an inorganic phosphorus-containing compound comprising, but not limited to, phosphates and polyphosphates. its preferably trisodium phosphate. Typically, an aqueous solution of trisodium phosphate of 60 g / L can be used, and heating to a temperature of about 60 ° C to boiling will help remove organic compounds as the fiber weights pass through the solution. Since inorganic cleaners are in most cases alkaline dissolved in water and the coating solutions are usually acidic, it is preferable to neutralize the pretreated yarns or ropes with dilute inorganic acid before immersing them in the electroplating solution. Hydrochloric acid and / or other mineral acids are suitable in aqueous solution.

In addition to the pretreatment in Part 8, the coating process must ensure that the surface of the graphite or fiber is kept free of organic compounds by excluding them from the electroplating solution or allowing only the presence of organic compounds capable of reduction to free sulfur on the cathodic surface. ). This improvement essentially involves the vigorous removal of conventional electroplating additives comprising or containing organic compounds, such as wetting agents such as sodium lauryl sulfate, chelating compounds and brighteners containing organic components. Saccharin, for example, is suitable as an organic granularity modifier (kir-1 (dipper) because cathodic saccharin has a rather unique ability to reduce to elemental sulfur.

in more detail, as described in pretreatment section 8, best seen in Figures 1 and 7, the apparatus consists of a trisodium phosphate cleaning section 26 followed by a rinsing section 30 and an acid cleaning section 34 followed by a second rinsing section 38. Each of the pretreatment sections 26, 30, 34 and 38 is provided with wash triangle arms 28, 32-32A, 36 and 40-40A, respectively, which are shown in detail in Figures 22-24. Each of the pretreatment sections 26, 30, 34 and 38 is also provided with a tank into which the effluent from the washing triangles 28, 32A, 32, 36, 40A and 40 flows. The trisodium phosphate purification section 26 and the acid purification station 34 have individual tanks 27 and 31, respectively. The flushing sections 30 and 38 each have two tanks, 33, 41 and 39, 49, respectively. In operation, the fibers 2 pass through the triangular arms 28, 32A, 32, 36, 40A and 40 in one direction, while the liquid passes through in the opposite direction.

A trisodium phosphate cleaning solution, which generally represents any suitable concentration, can be used in the cleaning section 26. However, practice has shown that 60 g of trisodium phosphate per 1 liter of water at 82 ° C provides the necessary cleaning for carbon fibers. Water is used in the rinsing section 30 to remove residual trisodium phosphate from the fibers 2, which 35 leave the trisodium phosphate section 26.

i I? 77900 The fibers then pass through a triple branch 36 in the acid cleaning section 34 as the acid solution flows countercurrently with the fibers 2. The acid suitable for pretreatment in combination with trisodium phosphate purification is a 10% hydrochloric acid solution. The fibers 2 are then rinsed with water in the rinsing section 38, where the water again enters through the upper part of the triangular branches 4Q and 40A and exits through the countercurrent part of the triangular opening passing countercurrently with the fibers 2.

As shown in Fig. 7, the pretreatment section 8 is combined to facilitate the pretreatment of the fibers 2 and to avoid or minimize the accumulation of contaminated pretreatment solution. Each pretreatment tank is provided with a vertical tube 308 having a basket filter 15 310 arranged over the opening. The tank outlet is pumped from each tank through a standpipe 308 by a pump 306. A line 316 from the standpipe 308 in the flush tank 49 communicates with the liquid supply point of the three branch 40A in connection with the flush tank 39. Line 326 is connected to the supply point of a three-to-two branch 40 connected to the reservoir 49 and the discharge line 320 is for draining liquid from the reservoir 39.

The recirculation line 314 extends from the vertical tube 308 in the tank 31 to the liquid supply point of the three branches 36 to recycle the hydrochloric acid oxygen. Feed point line 324 is used to deliver initial and fill hydrochloric acid washes to the liquid side of the three branches 36.

The flushing tanks 41 and 33 are provided with a line 325 to the liquid supply opening of the three-branch 32 connected to the tank 41 and from the vertical pipe 308 in the tank 41 to the supply point of the three-branch 32A connected to the tank 33. The discharge line 322 is for discharge from the tank 33.

The trisodium phosphate tank 27 is provided with both a 35 recirculation line 312 from a vertical pipe 308 to a three-way 77900 branch 28 feed point and a line 300 to supply initial and fill trisodium phosphate to the three-branch liquid supply point 28.

A neutralization tank 318 charged with a neutralizing agent 33Q, such as Dolomite, is provided in the system to receive the hydrochloric acid effluent from the flush tank 39 and the trisodium phosphate effluent from the flush tank 33.

In operation, the fibers 2 pass through the triangular branches 10 28, 32A, 32, 36, 40A and 40 as the liquid passes from the liquid supply points of the triangular branches to the fiber inlets upstream of the triangular branches. The trisodium phosphate wash is recycled through riser 308 and recycle line 312. The residue on the surface of the fibers 2, after passing through the three branches 28, is rinsed from the fibers 2 with clean water passing through the three branches 32 in connection with the rinsing tank 41 and with the outlet of the rinsing tank 41 passing through the three branches 32A, which is in connection with the flushing tank 33. The liquid in the rinsing tank 33 which becomes impure of trisodium phosphate is removed to the neutralization tank 318.

After the fibers 2 leave the rinsing portion 30, a hydrochloric acid wash is passed over the fibers 2 in the triple branch 36. The effluent of the triple branch 36 is recycled to the liquid feed opening of the triple branch 36 through a vertical pipe 308 in the tank 31 and a recycling line 314. The fibers 2 leaving the triple branch 36 are rinsed in the rinsing section 38. Clean water enters the rinsing section 38 through the triple branch 40, which is connected to the rinsing tank 49 and flows into the rinsing tank. The liquid from the rinse tank 30 is pumped along line 316 to the liquid supply point of the three branch 40A connected to the rinse tank 39 and conveyed over the fibers 2 to the rinse tank 39. The liquid in the rinse tank 39 is contaminated with hydrochloric acid and removed through line 320.

i9 77900

The nature of trisodium phosphate and hydrochloric acid together with a calcium-based material such as Dolomite; neutralizes the waste and minimizes the additional treatment required for the waste before it is removed as waste along line 328.

Next, the pretreated fibers 2 are electroplated. As seen in Figure 1, a large number of electrical coating tanks 16, 20, 22 and 24 are used in series. In the high voltage and high current conditions of the method, the series arrangement of the electroplating tanks 18, 20, 22 and 24 provides a means of providing separate voltage and current to the fibers 2 as a function of the accumulation of the metal coating fibers 2. Thus, depending on the amount of metal coating on the surface of the fibers 2, the coating voltage and the coating current can be set to levels that are most suitable for the specific resistance developed by the fiber and metal.

The electrolyte coating tank 18 is shown in Figures 8, 9 and 10 and is identical in construction to the coating tanks 20, 22 and 24 shown in Figure 1. The tank 18 2Q is arranged to retain the electrolyte bath. Attached to the container 18 are contact rollers 100 and anode support rods 102 arranged in a circuit. The contact rollers 100 receive current from the open rail 104 and the anode support rods 102 are connected directly to the open rail 106. Each of the coating tanks 25, 20, 22 and 24 is provided with similar but separate independent connections, as shown in Figure 22. The anode support rods 102 support anode baskets 110 to hold and transport current to nickel or other metal plating chips 30 Each tank 18, 20, 22 and 24 is also provided with heat exchangers 114 to heat the electrolyte bath to achieve the desired initial temperature at the beginning and to cool the electrolyte in the high intensity flow operation.

The tank is provided with a shaft 103 defined by a fixed wall 105 to which a surface control 107 is attached and a recycling line 109. The recycling line 109 comprises a pump 111 and a filter 113 and functions for continuously circulating electrolyte from the shaft 103 to the tank 18. Recycled under normal operating conditions the electro-5 lysate enters the tank 18 and causes the electrolyte in the tank to rise to a level above the wall 105 and flow into the shaft 103. Once the electrolyte has evaporated from the tank, the surface in the shaft falls and requires filling from the downstream flushing section 12 shown in Figure 26.

The container 18 is also provided with a line 132 and a pump bolt 134 through which the electrolyte is pumped to the main pipe 123, which distributes the electrolyte to the spray nozzle 130 above the contact rollers 100.

As seen in more detail in Figure 13, the threads 2 pass over the contact rollers 100 and intermediate rollers 112 located near the bottom of the container. The intermediate rollers 112 are used in pairs around which the fibers 2 pass in contact with the coming contact roller 100.

The rollers 100 in the container 18 communicate with the open rail 104 via a contact portion 118. A detail of the contact portion 118, shown in Figure 11, shows that the contact portions 118 consist of a copper rod 120 and multiple groups of phospho-25 ripron fingers 122 and 124, which together provide positive contact over a suitably large area on the contact roller 100 to avoid high resistance conditions. creating a contact point. The fingers 122 and 124 are resiliently attached to the rod 120 and, depending on the nature of the material, are driven into contact with the contact roller 100 continuously.

Thus, a high-strength positive electrical contact installation is provided for an environment where conventional brushed contacts cannot serve.

The high voltage high current method of the present invention is further facilitated by shielding the fibers 2 as they pass between the electrolyte bath and the various contact rollers. The system comprises a recycle spray system 126, generally seen in Figures 8 and 9, through which system the electrolyte is recycled from the coating tanks and sprayed through the spray nozzles 130 onto the fibers 2 at contact points on the contact rollers 100.

The spray nozzles 130 are arranged in two parallel tubular arms 136 and 138 with nozzle openings 139 located on their lower surfaces. As best seen in Figure 15, one tubular arm 136 of the spray nozzle 130 is arranged to direct the electrolyte tangentially to the surface of the fibers at the point where the fibers 2 leave the contact roll 100. The second tubular arm 138 of the spray nozzle 130 is arranged to feed the electrolyte immediately at the top of the contact roll 100. to the contact roll 100. As previously discussed, it is vital that appropriate tension is applied to the fibers 2 to ensure that the fibers 2 are held in a tight straight line between the contact rollers 100 and the intermediate rollers 112. The need for a tight line is due to the need to ensure that a low contact resistance suitable for current flow is available along with high conductivity fibers from the contact rollers 100 to the electrolysis bath. The electrolyte circulated over the contact rollers 100 and the fibers 2 provides a parallel resistor in the circuit and cools the fibers 2.

It is known that the fibers 2 that are coated have a low melting current, such as 10 amps for a 12K rope with a diameter of about 7 microns. However, the method of this invention requires about 25 amps between contacts or about 125 amps per fiber in each container.

In addition, both contact resistance and anisotropic resistance must be overcome. The contact resistance of an approximately 7 micron 12K rope with unmixed pure copper is 22,779,900 to about 2 ohms, i.e., 45 volts requires twenty-two and a half amps before coating occurs.

The anisotropic resistance is 1, Q00 times the longitudinal axis.

Thus, the total contact area must be 1,000 times the diameter of 5 ropes, which for 8. micron is 8.6 mm. Practice has taught that a 12 millimeter contact suitably provides the electrical requirements of the system when coating a 7 micron rope, thus using two and three inch contact rollers 100. It is also vital that the contact rollers 10 be located at a certain distance above the electrolyte bath to allow operating the system at the high voltages necessary to achieve the coating according to the method. In practice, it has been found that the contact rollers 100 have to be placed at a distance of 12 to 26 millimeters from the electrolysis bath when voltages of 16 to 25 volts are used. In addition, it has been found that a recycling of about 7.5 liters per minute per contact roller at a speed of about 0.46 to 0.76 meters / min cools the fiber appropriately and provides a suitable parallel resistance when more than 5,000 amps. passes through the system in three cells.

The electrolyte of the process is a solution consisting of 60-75 grams of metal, preferably in the form of N1Cl2 and NiSO4, per 1 liter of solution. The pH of the solution is adjusted to 4-4.5 and the temperature is maintained between 63-66 ° C. Recirculation of the electrolyte through the spray nozzles 130 at the desired rate requires that the nozzle orifices be approximately 2.4 mm in diameter at 3.2 mm centers along the lengths of each of the tubular arms 136 and 138. The presence of electrolyte in the fibers 30 is vital, but care must be taken to avoid an excessive amount of electrolyte, otherwise the contact roll will be subjected to coating in the electrolyte.

The anode support rod 102 for the anode basket 110 is shown in detail in Figure 20 and consists essentially of 23,77900 layers. The steel inner rod 150 provides structural support to the anode basket 110. A copper coating 152, such as a copper tube, over the steel rod 150 provides electrical properties desirable for current flow 5, and insulation made of some material, such as vinyl 154, insulates the entire anode support rod 102. At strategic points, vinyl is removed by rod 102 and cavities 156 expose copper cladding 152 to provide electrical contact.

As best seen in Figure 21, the anode basket 110 is provided with conventional openings 158 found in the anode baskets, but also has a vinyl insulated cover 162 extending from the top of the anode basket 110 below the surface of the electrolysis bath. It has been taught in practice that by isolating the anode basket 110 from four to twelve inches of the top, the anode basket 110 is protected from destruction of the protective oxide under the high intensity current and voltage conditions of the present invention. The conventional hooks 160 seen in the anode baskets 110 are arranged to fit into the recesses 156 located in the anode support rod 102. In addition, the anode basket is preferably made of titanium due to the nature of the high voltage environment and the electrolyte. A high voltage has been found to remove the surface of titanium, which is usually a TiCl 4 layer that protects the 25 anode baskets 110 from the electrolyte.

The contact rollers 100 are shown in detail in Figures 17-19. Each roller 100 is located in close proximity to the electrolyte in the coating tanks and is each adapted to carry a large current through the system in the vicinity of the highest voltage. The contact roller 100 is thus designed for repeated replacement. The contact roller 100 is provided with fixed end mounting portions 170 and 172 that retain the cylindrical copper tube 174. The cylindrical copper tube 174 is arranged to contact the commutator fingers 122-124 and supply current to both the fibers 2 and the recycled electrolyte to the electrolyte. The copper tube 174 is made of conventional L-copper, which must be able to carry 350 amps. The diameter of the tube is critical because the diameter dictates the contact surface fibers 2 and the distance 5 that the contact roll 100 must be from the electrolyte surface. As a result, the bases 170 and 172 are fixedly aligned with each other for releasably supporting the tube 174 of the contact roller 100. The base 170 is provided with a bearing support 176 through which the screw base 10 178 passes. The screw base 178 rotatably supports the copper tube 174 with the sleeve support 180 and has the ability to release the copper tube 174 upon contraction of the sleeve support 180 by removing the screw 178. The base 172 includes a sleeve support 182 on which the retainer 184 is formed. Each copper tube 174 is provided with a notched connection groove 186 which fits around the retainer 184 and provides a positive attachment of the copper tube 174 to the sleeve support 182, thereby avoiding uncertainty in alignment and facilitating the task of replacing each copper tube portion 174.

The overall electrical system 188 of the method and apparatus is shown schematically in Figure 22, which shows the ability to apply voltage and current separately to each electrolysis tank 18, 20, 22, 24. Conventional rectifiers 189, 191, 193 and 195 are used as DC current sources. to apply current to the respective contact rollers 100 in each electrolysis tank. For illustration, the open rails 104, 194, 196, 198 are seen extending from the rectifiers 189, 191, 193 and 195, respectively, to one of six contact rollers 100 in the electrolyte tanks 18, 20, 22 and 24. However, all six contact rollers 100 in each electrolysis tank are immediately connected to the same open rail. The open rails 106, 202, 204 and 206 are seen extending from the same rectifiers 189, 191, 193 and 195, respectively, through cables 2Q3 to a single anode support rod 102 attached to the electrolyte reservoirs 18, 20, 22 and 24. Again, 25 7 7 9 0 0 the anode open rails contact each anode support rod 102 attached to each electrolysis tank connected to the open rail.

As a result of the arrangement, a separate high-5 voltage can be supplied to each electrolysis tank 18, 20, 22 and 24 as a function of the metal coating on the surface of the fibers 2 in each electrolysis tank.

Practice has taught that in mass production, the voltage of the first tank 18 should not be less than 16 10 volts and rarely less than 24 volts. The voltage in the second tank 20 should not be less than 14 volts and the voltage in the third electrolyte tank 22 should not be less than 12 volts.

For example, the fibers 2 are coated in a system 15 formed by three rectifier-electrolyte tank assemblies, rather than the four seen in Figures 1 and 22, under the following conditions, resulting in an excellent coating:

Rectifier 189 191 193 20 Amps 1,400 1,400 1,400

Volts 45 26 17

Nickel-plated fibers 2 produced under these conditions have the following characteristics and features: 25 Thread shape Round (but dependent on graphite fiber)

Diameter 8 microns μm

Metal coating About 0.5 microns thick, about 50% of the total fiber weight 30 Density 2.50-3.00 g / cm ^ 2

Tensile strength up to 31,600 kp / cm 2

Tensile modulus 2.4 kp / cm Electrical conductivity 0.008 ohms / cm (12K rope) 0.10 ohms / 1000 fibers / cm 35 After nickel plating, the fully coated fibers 2 are delivered to the flushing section 12, as shown in Figure 1.

The stretching section 42 and the rinsing section 46 are provided with containers for collecting the effluent from the three arms 44, 44A, 44B, 48 and 48A and both to neutralize the effluent for waste removal and to provide storage space for collecting the filling for the electrolyte tanks 18, 20, 22 and 24.

As best seen in Figure 23, the tanks of the stretching section 42 10 consist of a cascade tank having separate compartments 252, 254 and 256. The cascade tank is a conventional three-station cascade countercurrent flushing tank manufactured by National Plastics, Thermal Electron Division. The cascade tank automatically takes care of the flow of the effluent from the 15-flow tanks to the counter-current tank by passing around the overflow dams 258. The liquid accumulated in the tank 256 can reach a level above the partition wall 255 between the tank 256 and the tank 254 and pass into the tank 254. Similarly, when the surface in the tank 254 is greater than the level of the partition wall 251, the liquid continues to flow countercurrently to the tank 252.

The flushing section comprises tanks 250 and 260. Both tanks 250 and 260 are provided with vertical tubes 268 having basket filters 270 with an opening at the top. The conveyor line 25 261 is connected to a vertical pipe 268 in the tanks 260 and is provided with a pump 264. The outlet of the tank 260 is pumped to a three branch 48A connected to the tank 250 to flush the fibers 2. The effluent from tank 250 is delivered along line 276 to the cascade tank assembly or alternatively along line 278 for waste disposal.

Line 271 connects the outlet of the tank 252 to tanks 18, 20, 22 and 24 equipped with level control devices 107 which open the solenoid valve 273 when the surface in the tanks 18, 20, 22 or 35 24 falls to a level requiring electrolyte.

27 7 79 0 0

In operation, the fibers 2 pass through triangular arms 44B, 44A, 44, 48A and 48 and are rinsed with water. Pure water is introduced into the system along line 267 to triangle 48 and flows against the direction of the fibers 2 to exit through the countercurrent end of column 5 to tank 260. The effluent from tank 260 is pumped to the liquid inlet of triangle 48A and discharged through the countercurrent end 250 to tank 250. from the previous rinsing treatment of the fibers 2, i.e. it can be disposed of as waste via line 278 or delivered to tank 256 if necessary. Tanks 256, 254, and 252 operate in a continuous recirculation mode to produce a liquid with an increasing electrolyte concentration. As a result, a minimum amount of contaminated water is produced in the system, while a solution rich in electrolyte is produced for electrolyte replenishment.

The triple branch, designated 28:11 and used in the system pretreatment section 8 and the flushing section 12, is shown in Figures 24-26. As previously shown, the triangular arms 20 are designed to provide a countercurrent flow of solution to the fibers 2. In practice, the three arms 28 are designed to have a countercurrent opening 210 and a downstream opening 212 for the fibers 2 to pass therethrough. The triangular arms 23 are also provided with a vault cover 214, 25 through which a solution, such as rinsing water, can enter and sow the fibers 2 as the fibers 2 pass through the triangular branch 28. The triangular arms 28 are also provided with a short pipe 216 which provides a hydrostatic pressure which directs the water upstream. In addition, the triangular arms 30 are designed to have an opening 210 for the passage of fibers 2 at a height slightly lower than the opening 212. Thus, the path along which water exits the triangular branch passes from the supply pipe 218 through the opening 21Q. The difference in the heights of the openings 210 and 212 and the presence of the short tube 216 in the downstream part of the triangular branch 28 cause the solution to flow countercurrently while the fibers 2 move downstream.

The device according to the present invention is arranged for synchronous operation as seen in Figures 27-29.

The motor 222 ensures that the contact rollers 100 and the guide rollers 51 rotate at the same speed to avoid abrasion of the fibers 2.

The motor 222 immediately drives an assembly of rollers 223 arranged to provide 10 traction rollers. The rollers 223 are located in the dryer 14 and, as best seen in Figure 29, cause the fiber to rotate in the other direction six times. The reversal suitably causes a force on the fibers 2 which pulls the fibers through the device without allowing play.

In addition, the motor 222 is connected via a gear and a chain to drive each contact roller 100 and each guide roller 51 at the same speed.

In essence, the gear and chain assembly consists of control drive assemblies 225, best seen in Figure 28, and contact roller drive assemblies 227. Each control drive assembly 225 comprises a drive gear 230 mounted on the arms 231, a gear 23 and a gear 224 fixedly attached. 230 and 224.

The contact roller drive assembly comprises a drive gear 239 attached to arms 231 common to gears 230, a gear 241 fixedly attached to each contact roller 100, and a chain 243 connecting both the gears 239 and each of the gears 30 241 to the six contact rollers each of the gears. in connection with the electrolyte tank.

As shown in Fig. 30, each guide roller 51 is provided with grooves 280 having conical sides 282 and flat surfaces 284. The diameter of the guide roller on the surface 35a 284 is the same as on the contact rollers 100 and the traction rollers 223, 29 7 7 9 0 0 i.e. the fibers 2 have a constant speed through the device.

The flat surfaces 284 cause the fibers or ropes 2 to spread, thereby facilitating either drying or wetting, depending on the desired effect.

5 The location of the traction rollers 223 in the dryer 14 improves drying. The flat surface and the force applied to the fibers 2 spread the fibers and thus accelerate the drying.

The system also includes a variable speed clutch drive motor 219 for the take-up reels 17. The force produced by the variable torque motor 219 provides the force with which the fibers 2 are drawn through the system. However, the traction rollers 223 provide a means of isolating the immediate force applied to the fibers 2 by the receiving coils 17 from the fibers upstream of the receiving coils.

The apparatus and coating method described above can be used to obtain tightly bonded metal coated fibers, not only for semiconducting fibers such as carbon or graphite fibers, but can also be used to form tightly bonded metal coatings on the surface of non-conductive fibers.

In more detail, it has been found that if the surface of strands or a large number of strands comprising a rough non-conductive core is sensitized and finally made conductive by chemically depositing a thin metallic interlayer, useful materials suitable for coating with the high voltage continuous apparatus described above and method. According to this aspect of the invention, metal-30 coatings provide strands with non-conductive cores in which the bond between the coating and the strand is so strong that bending of the fiber, such as in weaving or knitting, can break the coating but does not peel off. If a core with a soft surface, such as aramid, is used, it is necessary to roughen the surface before sensitizing the roughened surface with a noble metal salt, such as palladium. If a rough surface is normally present, such as cotton, roughening can be omitted. Next, a metal, such as nickel, silver or cuprous, is deposited on a rough, sensitized surface. In addition, the surface can be electroplated, for example with nickel or silver, using a high external voltage. In either case, smooth, continuous, tacky, thin metal coatings are obtained on the surface of the filaments. It is believed that the high voltage provides sufficient energy to cause uniform crystal embryo formation, especially if a large number of filaments are used. In addition, the high voltage provides an even distribution for each strand. The filaments of this invention comprising a thin metal-15 shell on the surface of a metallized core, and yarns, fabrics, blankets, and the like, can be knotted or folded without the metal substantially coming off as flakes.

According to this aspect of the present invention, there are provided continuous strands having a rough, electrically non-conductive polymeric core, the rough surface of which is sensitized to chemically precipitating a metal, an electrically conductive metallic interlayer chemically deposited on a sensitized rough surface of said shell. bonded thereto, alone, or in combination with at least one thin, flat, tightly bonded, electrically conductive layer of at least one metal electrically deposited on said intermediate layer. The bonding strength of the coated filament is at least sufficient to cause the coating to break but not peel off when the coated filament is bent.

In more detail, the core strands are usually selected from a large number of organic polymeric materials, all of which are electrically non-conductive. These include polyolefin fibers, for example, polypropylene-35, polyacrylonitrile, wool, cotton, rayon, and the like. Particularly disclosed are polyester filaments such as poly (ethylene terephthalate) and polyamide filaments such as nylons, for example poly (caprolactam) and poly (1,2-hexamethylenediamine dipia), and so-called aramids, which are long-chain synthetic polyamides. in which at least 85% of the amide bonds are attached directly to the two aromatic rings. The latter, together with their methods of preparation, are described in Encyclopedia of Chemical Technology, 3rd Edi-10 tion, Volume 3, John Wiley, New York, 1978, pages 213-242.

Particularly suitable core materials are aramid filaments prepared by polycondensation of diacid chlorides and diamines in amide solvents such as dimethylacetamide and N-methylpyrrolidone. Such high strength filaments can be prepared by solvent spinning of a condensation product of p-aminobenzoyl chloride hydrochloride, the product being known as poly (p-benzamide) or PPB. The second condensation product is prepared from p-phenylenediamine and terephthaloyl chloride. It is known as poly (paraphenylene terephthalamide) or PPD-T. Threads comprising the latter are available from DuPont Company, Wilmington, Delaware 19898 under the trade names KEVLAR 29 and 49, the latter being a hot drawn fiber. Typical bundles of strands used in this invention comprise an average of 4 thousand strands per bundle of yarns, each of which is 12 microns in diameter.

Referring to Figures 31 and 32, the continuous yarns and ropes used in the core 2 according to the present invention are commercially available. For example, suitable aramid fiber yarns are available from DuPont Company under the tradename KEVLAR-29 and KEVLAR-49 and suitable polyester fiber yarns are available from DuPont Company under the tradename DACRON-Polyester (Type 68). Suitable nylon polyamine-35 yarns are available from DuPont (Type 728) for example. Cotton yarn and wool fibers can be used. As mentioned above 32,77900, all such fibers are non-conductive and sensitized to chemical precipitation of the metallic intermediate layer 332. Cotton strands and wool fibers are naturally rough; the others must be made 5 rough.

The surface roughening is performed in any conventional manner, but the roughening of the strands with finely divided silica, alumina, sand, etc. In conventional strands, for example 4-15 microns 10 thick, 120 mesh abrasive produces a suitably roughened surface. The roughened surfaces provide substantial anchoring points for the intermediate layer 3, as seen in Figure 33, providing improved mechanical adhesion. In continuous production, roughening is facilitated by a mechanical Lei-15 fluidized bed test machine, for example a Cole-Parmer-type device.

The roughened fibers are then treated with materials to produce a sensitized and activated surface, for example, by continuously passing them through a solution of stannous chloride or stannous sulfate and then through a solution of a noble metal salt. Wetting of the roughened fibers in the stannous chloride solution can be facilitated by the addition of a small amount of detergent. The preferred noble metal salt is a water-soluble palladium salt such as palladium chloride. Salts of gold, platinum and rhodium can also be used. The sensitized rough surface provides an outwardly thin metal layer that catalyzes the chemical precipitation of the metal from the ions in the solution used to form the metallic interlayer, e.g., silver metal from silver nitrate solution, followed by rinsing, hydrazine, hydrazine compound or borohydride solution, borohydride , to reduce the silver ion to a silver metal that is well bonded to the surface. The thickness of the intermediate layer 35 332 develops with time and is thick enough 33 7 7 900 when the conductivity (or decrease in resistance) is sufficient to allow electrical deposition in the subsequent steps. This can be measured in known ways. For further details, reference is made to the above-mentioned US-3495940, the method of which, however, does not use a roughened fibrous surface.

The metal layer 334 is an electrically alloyable metal deposited by the high-voltage-high-current method as defined above. Two metal layers, or even 10 more, can be used and the metal can be the same or different metal, as seen in the working examples.

The roughening of the non-conductive fibers followed by the deposition of the metallic interlayer 334 may be accomplished as a separate process or may be made part of the line coating apparatus shown in Figure 1 by introducing a roughening portion 336, sensitizing and interlayer deposition portions 338, 340, 342 and 344. , shown schematically in Fig. 35, to the continuous line coating apparatus shown in Fig. 1, between the pretreatment cleaning section 8 and the electroprecipitation section 10.

The metal-coated filaments of this invention may be combined by any conventional means with the composites shown in Figure 34, wherein the matrix is a plastic, such as epoxy resin, or phenolic resin or the like, the matrix being reinforced by the presence of metal-coated cores 2.

Fig. 35 schematically shows the components of a continuous processing apparatus comprising in series a fiber conveying part, for example a roller 51, which feeds a 3Q mechanical fluidized bed consumption machine 336 in which the surface 2 of the fiber 2 is roughened, for example with 120 mesh silica slurry. This is not used if the fiber usually has a rough surface. After sensitization, for example by transporting and immersing 35 first in a tank 338 with a SnCl 2 solution, rinsing, and then in a tank 340 with a PdCl 2 solution, and 34 7 7 9 0 0 by rinsing a strand 2 with a coarse , the sensitized surface is conveyed to a tank 342 having a chemical metal precipitation bath containing, for example, silver nitrate and finally, without rinsing, to a reduction bath tank 338, 5 containing, for example, hydrazine hydrate (alkaline). A thin layer of silver is deposited, which layer is sufficient to reduce the electrical resistance at the point where the filament can be used in the composites or possibly sent to the electroprecipitation section 10 in Figure 1.

As mentioned above, it may be desirable to finish the metal-coated fibers produced by the process of this invention in a post-treatment finishing step. The post-treatment finishing process can be performed independently, however, it is preferred to perform the post-treatment finishing of the metal-coated fibers as part of the continuous line process illustrated in Figure 1, as part of the drying step 14 seen therein.

J. a post-treatment method and apparatus, essentially 20 treats metallized fibers, e.g., fibers, with a finishing material or materials that give them various properties, such as lubricity and thickness, and improved miscibility with plastics, and improved resistance to moisture, e.g., mixed with polymers. with.

For convenience, the following treatment applies to metal-coated fibers, although it should be understood that metallic filaments may also be treated.

In more detail, as seen in Figure 40, the finishing and drying apparatus and method comprises the steam portion shown in Figure 1, the finishing portions 366, the heating groups 364, and the receiving coils 17 shown in Figure 1 in portion 16. As will be described later, the portion 366 may comprise a single tank and one or more heating groups 364 may be used. In addition, apparatus 55 for providing an oxidized surface, such as low pressure steam distribution boxes, may be included.

As seen in Figure 40, in one embodiment, the finishing member 366 further comprises a first container 346, a second container 348, and a third container 5 350, all of which contain finishing solutions and facilitate the continuous flow of metal-coated fibers therethrough. Each container 346, 348 and 350 is provided with intermediate wheels 352 and 354 located close to the bottom of the container. The rollers 352 and 354 are cylindrical 10 and the guide roller 356 has a flat bottom to facilitate rope spreading and smooth finishing. Each container is provided with used contact rollers 356 and 358 located above the container in a superimposed row with intermediate wheels 352 and 354. The guide rollers 358 are also located at the inlet of each tank.

The heating section 364 consists of devices for heating the finished metal-coated fiber to dry and place the finishing solutions or emulsions on the metal-coated carbon fiber. As indicated, each tank may be followed by an independent heating section 364.

The drive for assembly is provided by a motor 360 which transfers the drive immediately to the take-up reel 17 and a chain drive consisting of chains 362 from which the force 25 is transferred from the traction roller gear 368 to the contact roller 358.

In use, the metal-coated fibers 2 pass through an air blowing section 53, as seen in Figure 1, and pass through steam distribution boxes 55, as seen in Figures 1 and 40, which oxidize the metal coating on the surface of the fibers. The metal-coated surface-oxidized fibers 2 first preferably pass through a reservoir 346 filled with a coupling / finishing agent, such as an aminosilane solution. After passing through the container 346, the metal-coated fiber is substantially provided with a coupling / -35 finishing surface coupled to the metal oxide surface of the coated fiber. The fiber 2 is then fed to a container 348 containing a filler / finisher such as a polyvinyl acetate solution. The polyvinyl acetate solution, together with the coupling / finishing, for example an aminosilane coating, gives a bulk density to the metal-coated fibers. Alternatively, both finishes can be combined in one container. The fibers 2 are then fed to a tank 350 where a finishing / lubricating agent, for example a polyethylene solution or emulsion, imparts lubricity to the fibers. Alternatively, this can be combined in one container with the finishing / coupling and / or finishing / bulk density agent.

The finished fibers 2 are then fed to an oven section 364 where drying and setting take place and the heated dry fibers 2 are passed to a second finishing section 366 and a drying section and finally wound on receiving coils 17. Although double steps are visible, for flexibility, depending on conditions, only one step is used.

With respect to the coupling / finishing component, this typically comprises a surface reactive coupling agent. Typically it is silane or titanate. The general formula for silanes is Y-R-Si-X 1, where X represents a hydrolyzable group, for example alkoxy; Y is a functional organic group such as methacryloxy, epoxy, etc., and R is typically a small aliphatic bond, - (CH 2) -, which attaches the functional organic group to the silicon (Si) at the stagnal position. Examples of available silanes are: vinyltriethoxysilane, vinyl-tris (beta-methoxyethoxy) silane, 3q gamma-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, n-beta- (aminoethyl) gamma-aminoethyl) gamma-ureideppropyltriethoxysilane, gamma-chloropropyltrimethoxysilane, gamma-mercaptopropyl-35 trimethoxysilane, and the like. Aminosilanes are preferred. All can be used in conventional amounts and in conventional media, such as those supplied or diluted with water or an organic solvent, or even as a dry concentrate, for example in a fluidized bed.

Typical titanates are isopropyl tri (dioctyl pyrophosphate) titanate, titanium di (dioctyl phosphate) oxyacetate and tetraoctyloxytitanium (dilauryl phosphite).

In practice, it has been found that aminosilane solutions containing 0.1-2.5 parts of gamma-aminopropyltriethoxysilane, such as Dow-Corning Z-6020, or gamma-Gly-cidoxypropyltrimethoxysilane, such as Dow-Corning Z-6040, per 100 parts of water adjusted to a pH of 3.5 to 8, for example with acetic acid, are particularly suitable for coupling aminosilanes to nickel- or silver-coated carbon or aramid fibers. Practice has shown that the time the fiber is in solution must be at least suitable for providing a surface with a coupled finishing agent. This is usually about 0.5 seconds, 2Q but the time may be longer, for example at least about 5 seconds, depending on the downstream residence time requirements.

As for the filler / finisher, this can usually be an organic polymeric material which is conventional for this purpose. Preferably it is a vinyl polymer or cellulose compound dissolved in water or an organic solvent, or emulsified in water. Suitable polymers include starches, cellulose ethers, esters and carboxylates. In addition, polyvinyl esters such as polyvinyl acetate and co-polymers such as ethylene / vinyl acetate, as well as polyvinyl alcohol and dispersants such as polyvinylpyrrolidone can be used. It is preferable to use polyvinyl acetate. All are used in amounts that have been found and known to be suitable for finishing purposes.

35 Practice has also taught that a solution of polyvinyl acetate containing about 20 parts of carboxylated polyvinyl acetate latex (Borden's Polyco 2142, 50% solids) per 100 parts of water provides a particularly good solution to contribute to the coating of metal-coated fibers. the bulk density. The residence time of the fiber in the polyvinyl acetate medium should be at least sufficient to provide a finished surface, preferably at least about 5.0 seconds.

Lubricity is provided by lubricants or lubricants comprising organic materials commonly used.

Preferably, molecular expressions are formed between the finished fibers and the surfaces against which they are moved, for example, intact plastic pellets. Such a feature reduces the tendency to wear. Examples of lubricants are fatty alcohols, fatty acid esters, glycerol partial esters, polyesters, fatty acid amides, for example oleamide, metal soaps, fatty acids, for example stearic acid, and polyolefins, especially polyethylenes, which are preferred. These can be used in the form of solutions and emulsions.

A polyethylene emulsion of 10 parts polyethylene (Bercen, Inc.'s Berzine S-200, 50% solids) in 100 parts water by weight provides a particularly desirable solution to provide lubricity to the fibers. A residence time of the fibers sufficient to provide a lubricated surface is used. A period of at least about 5 seconds has been found to be desirable in a polyethylene medium.

The method of producing an oxidized surface on a metal-coated fiber usually comprises exposing the outer surface to an oxidizing medium. The metal surface, of course, is one that is capable of oxidation. Chemical or atmospheric techniques, or the like, can be used with, for example, nickel, tin, copper, brass, and the like, and the use of heat is recommended because the rate of production of the oxide layer on the surface is improved. It is particularly suitable to use air or an oxygen-containing gas as a medium for oxidation and to use steam as a heat source. A suitable time is used to produce a metal oxide coating, preferably a flat, thin coating. In a continuous process using steam and air, only a fraction of a second is preferred, for example about 0.5 seconds, although a shorter or longer time may be allowed. For best results, the strands are dried before finishing.

Finished and / or oxidized metallic filaments made by this method have been used as a staple material for mixing with plastics, for example, from about 5 to 50% by weight in nylon, polyesters, polycarbonates, polyolefins, polyurethanes, poly-15 styrenes, polyepoxides, and the like. and a plastic matrix. If the strands are woven, knitted or assembled into carpets, laminates can be obtained. It has been found that finished metal-coated carbon fibers can be more easily mixed with plastic without great difficulty due to the increased bulk density of the finished, truncated material. Testing has shown that composites made from 60 parts silane-finished fibers of this invention and 40 parts by weight epoxy resin and 25 resin curing are 30% better based on the shear strength of the short beam at room temperature and elevated humid temperature than those made with unfinished fibers.

Fibers that have been finished and / or have a surface 30 oxidized in accordance with this invention have also been woven into fabrics. It has been found that the entanglement of fibers, which usually occurs occasionally in a metal-coated fiber, does not interfere with weaving after finishing has taken place. In addition, the woven material can be formed into a fabric very easily on the basis of lubricity, which is an essentially finished material. On the contrary, finished nickel-plated carbon, graphite, or other high-strength fiber has been found to have excellent lubricity and lacks abrasive ability, facilitating weaving. The finished fibers also avoid the splinting of random fibers from the fibers, which random fibers can cause the accumulation of fluffy material, which greatly impairs weaving by landing on guides in machines, etc.

10 In addition, finishing materials can act as water transfer agents that reduce the tendency of composites made from coated fibers to discharge after being placed in a plastic material and exposed to moisture.

It has been taught in practice that a carbon fiber coated with nickel and treated with steam, for example steam of distilled water, produces a surface of nickel oxide, dense and sticky, 150-500 nanometers thick, which is particularly compatible with aminosilane, and this is very suitable for producing with polymers composites with desirable properties.

The following examples illustrate this invention but are not intended to limit it.

Example 1 25 Four ropes (bundles of fibers) with 12,000 strands, each of 7 micron graphite fibers, were continuously drawn through a solution of 60 grams / liter of trisodium phosphate heated to 82-93 ° C and then through two flush tanks.

3Q The drain of the second flush tank was returned to the first. The ropes were then passed through a neutralization tank containing a 10% aqueous solution of CP hydrochloric acid (35%), then through two rinsing tanks. The effluent from the second flush tank was returned to the first, and the waste from all 35 tanks was combined for self-neutralization.

4i 77900

The continuous electroplating system used a coating solution having the following composition: Ingredients Amount

Nickel sulphate (NiSO 2 · 61 ^ 0) 300 g / liter Nickel chloride (NiCl 2 * 61 ^ 0) 90-150 g / liter

Boric acid (H 2 BO 2) 37-60 g / liter

The bath was then heated to 60-71 ° C and had a pH of 3.8-4.2.

The anode baskets were kept filled with electrolytic nickel pellets 10 and four ropes (fiber bundles) with 12,000 strands each of 7 micron carbon fibers cleaned of organic contaminants as described above were continuously drawn through the bath at a rope speed of 1.5 m / min and 120 amps. at a current of 15 amperes per 1000 fibers in total. The voltage drop from anode to cathode was 30 volts. At the same time, the electrolyte solution was circulated through the loop into contact with the rope entry and exit paths. Next, the rope was continuously passed through its identical bath, at a rope speed of 1.5 meters / min at a current of 180 amps. The final product was a rope consisting of the high strength fibers of this invention comprising a 7 micron fiber core and about 50% by weight of the coated fiber of crystalline electrospecified nickel tightly attached to the core. The metal cover was flat and had no exposed spots.

When the fiber was sharply bent and then examined, no peripheral cracking was observed in the metal sheath on the tensile side of the 30 bends. The rope could be twisted or tied in a knot without causing the coating to come off as a powder.

Example 2

When the procedure of Example 1 was repeated with a dowel graphite rope passed through 1.1,1-42,779,000 trichloroethane hot liquid and condensable vapors in a degreaser to purify them of organic matter, uniform metal coatings were finally obtained.

5 To illuminate the adverse effects of the organic compounds, when the concentration of organic impurities was allowed to accumulate in the degreaser of Example 2, the organic substances redefined the graphite fibers and the nickel coating became uneven. When the tri-10 sodium phosphate purification bath of Example 1 was replaced with wetting agents containing organic compounds (Wyandotte BN Purifier, Oakite 190 Purifier, or Ivory Liquid Detergent), the final nickel coating was not uniform.

Example 3 15 A continuous rope consisting of smooth-surfaced aramid fibers (4000 fibers per bundle, average 12 microns in diameter, poly (paraphenylene terephthalamide), DuPont KEVLAR-49) was mechanically rubbed with 120 mesh of silica slurried in water, gas-suspended in water. until the surface of each fiber was roughened. The rope was immersed in an aqueous solution containing 10 g / l of stannous chloride and 10 ml / l of concentrated hydrochloric acid, heated to 60 ° C, and allowed to stand there for one minute, and rinsed. The rope was then immersed in an aqueous solution containing 2.8 g of palladium chloride and 10 ml of concentrated aqueous hydrochloric acid per liter, heated to 60 ° C and allowed to stand there for one minute, and rinsed. This technique was repeated and a rough sensitized surface was obtained for the fibers. Next, the rope was immersed in an aqueous solution of silver nitrate containing 31 g / l of silver nitrate and then, without rinsing, in a solution of 85% aqueous hydrazine hydrate (Hummel Chemical Corp., No. 85). The silver interlayer then precipitated tightly. The sample was taken, washed and dried, and the resistance was measured with a resistance meter. If necessary, the silver precipitation procedure was repeated until the resistance of the 4K, 12 micron rope 43,77900 decreased to 65 ohms per meter, making it suitable for electroprecipitation.

In the continuous electroplating system, a coating solution having the following composition was used: 5 Ingredients Amount

Nickel sulphate (NiSO 4 * 61 2 O) 300 g / liter

Nickel chloride (ΝΐΟ ^ 'βΙ ^ Ο) 90-150 g / liter

Boric acid (H 2 BO 2) 37-60 g / liter

The bath was heated to 60-71 ° C and had a pH of 3.8-4.2.

The anode baskets were kept filled with electrolytic nickel pellets and four ropes (fiber bundles) with 4000 strands, each of which was a 12 micron carbon metallized aramid strand, were continuously drawn through the bath at a rope-15 speed of 1.5 meters / min. while using an external 30 volt external voltage with a current of 160 amps. At the same time, the electrolysis solution was circulated through the loop into contact with the rope entry and exit paths. Next, the rope was continuously passed through an identical bath 20 at a rope speed of 1.5 meters / min at a current of 160 amps. The final product was a rope composed of the high strength composite fibers of this invention comprising a 12 micron fiber core, a thin silver interlayer, and about 50% by weight of composite weight of crystalline electrodeposited nickel tightly adhered to the core through the interlayer.

If the thread is bent sharply, such as when weaving or knitting, and then examined, the metal cover may break, but it will not peel off.

Claims (44)

77900 44 A method of electrically coating fibers with metal, the method comprising: (a) continuously passing the fiber (2) through an electrolytic solution in a container (18) in which a metal anode (110) is embedded; (b) conveying a direct current through the fiber (2) to the anode by supplying said current to the fiber at a point of contact immediately preceding the surface of the electrolyte reservoir; (c) maintaining the voltage across the electrolyte from the fiber (2) to the anode (110) above 16V; (d) cooling the fiber (2) from the point of contact to the electrolyte, wherein the metal from the anode travels to and adheres to the fiber 15, characterized in that the method further comprises the steps of: (a ') continuously conveying the metal-coated fiber (2) to a second electrode (20); through a lithium solution embedded in the grain metal anode 20 (110); (b *) directing a direct current through the metal-coated fiber (2) to the anode (110) in the second container (20) by supplying said current to the fiber at a point of contact immediately before the surface of the electrolyte 25 in the container; (c ') adjusting the voltage across the electrolyte from the fiber (2) to the anode (110) to a value above 14 V as a function of the resistance generated by the metal-coated fiber in the second container (20); and 30 (d ') cooling the fiber (2) from the point of contact to the electrolyte, wherein the metal from the anode is further transported to the metal-coated fiber, further coating the metal-coated fiber, and the method further comprising the steps of: 35 (a ") transporting the metal-coated fiber (2) continuously from the second electrolyte reservoir (20) through a third electrolyte solution in the third reservoir (22) embedded in the metal anode (110); (b ") directing direct current from the metal-coated fiber (2) to the anode (110) in the third reservoir (22) by feeding said current to the fiber at a point of contact immediately before the surface of the electrolyte in the reservoir; (c ”) adjusting the voltage in the third electrolyte from the fiber (2) to the anode (22) to a value above 12 V as a function of the resistance developed by the metal-coated fiber in the third reservoir (22); and (d ") cooling the fiber from the point of contact to the electrolyte, wherein the metal from the anode (110) in the third container (22) passes to the metal-coated fiber (2), further coating the metal-coated gold. Method according to Claim 1, characterized in that the voltage at point (c) is above 24 V 20. A method according to claim 1, characterized in that the voltage in the first tank (18) is about 45 V and the current is about 1400 A; the voltage in the second tank (20) is about 26 V and the current is about 1400 A; 25 and the voltage in the third tank (22) is about 17 V and the current is about 1400 A. The method according to claim 1, characterized in that it further comprises continuously conveying the metal-coated fiber (2) obtained in step (d ") through the electrolyte solutions in at least one successive additional tank (24) arranged in a row and embedded with metal anodes ( 110), wherein a direct current passes through the metal-coated fiber (2) to the anode, and that each container is further electroplated with metal to further coat the metal-coated fiber 46 7 7 9 0 0. The method of claim 1, further comprising pretreating the fiber to purify the fiber prior to feeding it to the electrolyte 5. A method according to claim 5, characterized in that the pretreatment of the fibers consists of the steps of: (a) conveying the fibers countercurrent to the trisodium phosphate solution; and (b) conveying the fibers leaving the trisodium phosphate wash via rinsing. A method according to claim 6, characterized in that the pretreatment further comprises conveying the fibers (2) upstream via a hydrochloric acid wash; and rinsing the fibers with water after washing with hydrochloric acid. Process according to Claim 6, characterized in that the trisodium phosphate solution is a mixture of 226.8 g of trisodium phosphate per 3.785 l of water at 82 ° C. Process according to Claim 7, characterized in that the hydrochloric acid solution is a 10% hydrochloric acid solution. A method according to claim 1, characterized in that a plurality of fibers are conveyed through the system in parallel arrangement and simultaneously coated with metal. A method according to claim 10, characterized in that the contact at the point of contact is a contact roller (100), and that the method further comprises rotating the contact roller (100) in the direction of the fiber (2). Method according to Claim 1, characterized in that the cooling of the fiber (2) is carried out by circulating the electrolyte over the fiber at the point of contact J 47 7 7 9 0 0. A method according to claim 12, characterized in that it comprises injecting the recycled electrolyte onto the fiber both at the point where the contact adhesion first takes place and at the point where the contact is separated. A method according to claim 1 or 4, characterized in that it further comprises rinsing the metal-coated fiber after the completion of the metal coating 10. A method according to claim 14, characterized in that the metal-coated fiber is rinsed with water running in the opposite direction to the flow of the fiber. The method of claim 15, further comprising steam treating the rinsed metal-coated fiber. A method according to claim 16, characterized in that it comprises drying the metal-coated fiber with a steam treatment. A method according to claim 17, characterized in that it comprises winding a metal-coated fiber on traction rollers (223). A method according to claim 18, characterized in that the traction rollers (223) provide a driving force for conveying the fiber through the system. The method of claim 1, characterized in that cooling the fiber through which the electric current passes comprises the steps of: (a) continuously passing the fiber over an electrically conductive surface located above the electrolyte reservoir to the electrolyte reservoir; and (b) directing the cooling medium to the fiber at a point where the fiber adheres to the current carrying surface, 35 and at a point where the fiber differs from the current carrying surface. A method according to claim 20, characterized in that the current-carrying surface is a first contact roller (100). A method according to claim 21, characterized in that the cooling medium is an electrolyte recycled from the electrolyte tank. The method of claim 22, further comprising directing one recycled electrolyte jet to a center point on the contact roller (100) and directing the second jet tangentially downward to the fiber (2) at a location on the contact roller (100) closest to the electrolyte reservoir. The method of claim 21, further comprising continuously conveying the fiber from the electrolyte reservoir over the second contact roll for further processing; directing the coolant over the first contact roller at a point where the fiber adheres to the first contact roller and tangentially downward at the point where the fiber detaches from the first contact roller, tangentially downward at the point where the fiber adheres to the second contact roller and directly over the second contact at the point where the fiber 25 differs from the second. An apparatus for metal coating a fiber, the apparatus comprising: (a) a current rectifier (189); (b) an electrolyte reservoir (18) to which the rectifier 30 supplies current; (c) an electrolyte in the electrolyte reservoir (18); (d) a metal anode (110) in the electrolyte; (e) means (51) for continuously passing the fiber (2) through the electrolyte; (F) means (100) for supplying direct current from the rectifier 77900 49 to the fiber (2) at a point of contact immediately prior to the surface of the electrolyte in the reservoir (18); (g) means for maintaining the voltage between the fiber and the anode above 16 V.; and 5 (h) means for cooling the fiber from the point of contact to the electrolyte, characterized in that the device further comprises: (a ') a second rectifier (191); (b ') a second electrolyte reservoir (20) to which current is supplied by the second rectifier (191); (c ') electrolyte in the second electrolyte reservoir (20); (d ') a metal anode in the electrolyte in the second electrolyte reservoir (20); (E ') means (51) for continuously conveying the metal-coated fiber from the first electrolyte tank (18) through the second electrolyte tank (20); (f) means (100) for supplying direct current from the second rectifier (191) to the fiber (2) at a point of contact immediately before the surface of the electrolyte in the second electrolyte reservoir; (g ') means for maintaining the voltage between the metal-coated fiber (2) and the anode (110) in the second electrolyte reservoir (20) above 14 V as a function of the resistance generated by the metal-coated fiber (2); and (h ') means for cooling the fiber from the point of contact to the electrolyte, said device further comprising: (a ") a third rectifier (193); (b") a third electrolyte reservoir (22) to which the third rectifier (193) supplies current; (c ”) electrolyte in the third electrolyte reservoir (22); (E ") means (51) for continuously conveying the metal-coated fiber from the second container (20) through the electrolyte in the third container (22); 5 (f ") means (100) for supplying direct current from the third rectifier to the third electrolyte reservoir (22) via a metal-coated fiber (2) at a point of contact immediately before the surface of the electrolyte in the third electrolyte reservoir; 10 (g") means in the third electrolyte reservoir and to keep the voltage between the anode above 12 V; and (h ") means for cooling the fiber from the point of contact to the electrolyte. Device according to claim 25, characterized in that the voltage across the fiber and the anode is about 24 V. The apparatus of claim 25, further comprising: 20 (a) four or more rectifiers (189, 191, 193, 195); (b) four or more electrolyte tanks (18, 20, 22, 24) to which four or more rectifiers supply direct current; (C) electrolyte in each of the four or more electrolyte reservoirs (18, 20, 22, 24); (d) a metal anode (110) in the electrolyte of each of the four or more electrolyte reservoirs; (e) means (6, 51) for continuously conveying the metal-coated fiber 30 in the four or more electrolyte tanks; (f) means (100) for supplying direct current from the respective rectifier (189, 191, 193, 195) to the metal-coated fiber (2) at a point of contact immediately before the electrolyte surface in each of the four or more electrolyte tanks; (g) means for maintaining the voltage between the metal-coated fiber and the anode in four or more containers (18, 20, 22, 24) at a voltage determined as a function of the resistance following the metal-coated fiber; and (h) means for cooling the fiber from the point of contact to the electrolyte in each of the four or more containers (18, 20, 22, 24). Device according to claim 25, characterized in that it further comprises means (8) for pretreating the fiber before feeding it into the first electrolyte tank (18). Device according to claim 28, characterized in that the means (8) for pretreating the fiber before feeding to the first container (18) consist of a washing triangle (28, 32, 32A, 36, 40, 40A), means (51) for conveying the fiber continuously through the wash triangle and means (306, 312, 314, 316) for conveying trisodium phosphate through the wash triangle in a direction opposite to the direction of travel of the fiber therethrough. Device according to claim 29, characterized in that the washing triangle branch (28) consists of: (a) an inner chamber for the passage of fiber therethrough; (b) an inlet (210) for the fiber to enter the three branches; (c) an outlet (212) for exiting the fiber from the three branches, the outlet (212) being higher than the inlet (210); and (d) interfering means (216) for directing the tri-sodium phosphate flow introduced into the triple branch outwardly through the fiber inlet (210). Device according to claim 30, characterized in that the interference means in the washing triangle branch is a tube (216) extending inwards from the inlet opening (210) to the center of the chamber. The device of claim 25, further comprising means for mounting a plurality of fibers to be fed into the electrolyte in parallel. Device according to Claim 32, characterized in that the means for mounting the fibers πηλοί 0 consist of: (a) a horizontally arranged rail (56); (b) rail means (54) for mounting a plurality of fiber halves; (c) a second rail (60) horizontally above and aligned with the first rail; and (d) guide means (59, 62) on the second rail portion (60), the guide means being moved adjacent to each other, spaced apart from each other, the fibers (2) passing from the spool 20 on the first rail (56) by a guide roller (62) , which is vertically substantially aligned with the spool, over the electrolyte coating system in parallel at a distance from each other. The apparatus of claim 33, further comprising means for winding the coated fibers and providing a driving force for transferring the fibers through the process device. Device according to claim 34, characterized in that the means for winding the fibers and providing a driving force consist of a motor (219, 30 222) driving a plurality of rollers (17), each arranged to wind a single fiber, and a group of traction rollers (223) , which are rollers (17) in the opposite direction, arranged to reverse the direction of the fiber and thus prevent the fibers from loosening. Device according to claim 35, characterized in that it comprises means (12) for rinsing the metal-coated fibers leaving the last metal coating container (24). Device according to claim 36, characterized in that the means for rinsing the metal-coated fibers consist of a plurality of washing triangle branches (43A, 44, 44A, 44B, 48) arranged for the passage of the fiber (2) through them in one direction, and through them for the passage of water in the opposite direction to the direction of travel of the fiber. Device according to claim 25, characterized in that it has means (130) for injecting a medium onto the fiber (2) through which the electric current passes, the means comprising: 15 (a) a first pipe section (136) having an array of nozzle openings (139) ) on the lower surface, the nozzle openings being directed in the first place to the fiber (2); (b) a second tube portion (138) having an aligned array of nozzle openings on the lower surface, the nozzle openings 20 being directed to a second location on the fiber; (c) means (128) for supplying medium to the first (136) and second (138) tubular portions, said apparatus further comprising means (112) for continuously conveying the fiber from the contact rollers (100) to the electrolyte solution; means (126) for directing electrolyte to the first tube portion and over the fiber at the point where the fiber (2) adheres to the contact roller (100), and means (126) for directing electrolyte to the second tube portion and over the fiber at the point where the fiber (2) differs from the contact roll (100); ). The apparatus of claim 38, further comprising means (132, 134) for circulating the electrolyte from the electrolyte into which the fiber passes to the first and second tubular portions (136, 35 138). 54 77900 Device according to claim 39, characterized in that the contact roller (100) is cylindrical and adapted to rotate; that the fiber (2) is in contact with 1/4 of the surface of the contact roller; that the first tube portion (136) is arranged above and aligned with the contact roller (100) at a location directly above the center of the contact roller (100) where the fiber adheres to the contact roller to direct the electrolyte directly onto the contact roller, and that the second tube portion (138) 10 is positioned above the contact roller (100) at a distance of 90 ° from the point to which the first tube section (136) directs the medium, and positioned to direct the electrolyte to the fiber tangentially to the contact roller (100). The device of claim 40, further comprising an electrolyte reservoir (18); a plurality of contact rollers (100) mounted in series at the top of the electrolyte reservoir (18), through the contact rollers (100) of which the fiber (2) passes and through which direct current is supplied to the fiber; an electrolyte in the electrolyte reservoir at a level very close to the bottom of the contact rollers (100); means (5, 112) for conveying the fiber first over the first contact roller (100) to the electrolyte, then from the electrolyte to the second contact roller immediately downstream of the first contact roller, and then continuously over the contact rollers positioned thereafter so as to pass over the contact roller to the electrolyte and over the next roll of electrolyte. Device according to Claim 25, characterized in that it consists of an electrolytic tank (118); the electrolyte in the tank; rotating contact rollers (100) attached to the top of the container and over which the fiber (2) is adapted to pass immediately before the surface of the electrolyte in the container; 35 carrier rollers (112) located at the bottom of the electrolyte reservoir and aligned with the contact rollers (100) so that the fiber (2) passes around them; rectifier; a busbar (104) extending from the rectifier to the electrolyte reservoir; and an electrically conductive rail (120) extending from the busbar (104) to the contact roller (100); a plurality of conductive fingers (122,124) extending from the electrically conductive rail (120) to contact with the contact roller (100) and means (130) for cooling the fiber (2) from the point of contact to the electrolyte. Device according to claim 42, characterized in that the group of conductive fingers consists of two rows (122, 124) of elastic fingers, the row (124) closest to the contact roller (100) being shorter than the second row (122), wherein both The ends of the 15 rows rest against the touch roller (100). Apparatus according to claim 42, characterized in that the fiber cooling means (130) comprises means (136) for directing the electrolyte onto the contact rollers (100) at the point where the fiber (2) engages the contact rollers. 56 7 7 9 0 0