DE1939339A1 - Process for the production of sheathed or sheathed fibers - Google Patents

Description

PATENT LAWYERS DJPU-INe-CURTWALLACH 8 Munich 2 *. <

OIPL-ΙΝΘ. GÜNTHER KOCH. .- ^! 2L _er ** n

DR. Tl NO H Al BACH ™ ^ mZ2 ™ 7 "^ ™ *

12169 - H / We

ROLIS-ROYCE LIMITED, Derby / England

Process for the production of coated or coated fibers

The invention relates to a method for producing wrapped or coated pasers as well as for the production of a Composite material from this.

In recent years, significant efforts have been made on the Development of fiber-reinforced matrix materials related; There is particular interest in the use of materials with metal as matrix material, which when used in conjunction with a high temperature-resistant reinforcing fiber material such as for example aluminum oxide, silicon carbide, boron or Carbon fibers operate at relatively high temperatures endure. A major problem in the manufacture of such a composite material was the creation of methods for embedding the reinforcing fibers in the matrix metal, , without the reinforcement fiber high temperatures or to expose mechanical stresses, which are their properties

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could destroy. This is especially true in the case of Von Carbon fibers, due to their fineness and variety particularly sensitive to such in a tow rope Are impairment.

The present invention is intended to provide a method for producing a coated or sheathed fiber created -. .-will, whereby the application of one at ■ proportionate low temperature feasible process-with-high

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Scattering power is made possible.

W To this end, in a method zxxr preparation of a coated or »the invention coated or clad fiber provided according to the ,, by heating the fiber, and then a suitable zersetsbaren metal-containing vapor in contact with the Faseroberfläehe brings the temperature of the fiber is selected so is / that the vapor decomposes on its surface with the formation of a metal deposit.

Preferably a vapor of an organometallic compound is used; a preferred Aüsführungsform the invention provides for the deposition of aluminum-front of a vapor of an organo-metallic compound wiebeispielsweise ^ y triisobutyl aluminum (TIBA).

in this case, the heating of the fiber takes place preferably in the way that you get radiant heat on "the fiber material directs.

The warming or heating is preferably carried out in a closed oven in which an atmosphere is kept atifredisr, which contains the organometallic vapor in an inert carrier gas * ^; ';^;'■-' ■ _·: - ~ -

Preference is given to the decomposing toid separation in continuous ^ "

in any other way; .. for example, a paser or a strand of fibers passed through the furnace in which the deposit decomposition takes place *

In case the production of one from the thread-like fiber material .wound structure is desired, it is preferable if the winding takes place in the deposition chamber in such a way that that the deposition and the winding up "simultaneously in front of you go, creating a coherent matrix body, in which the wound reinforcement fiber is embedded ο -

Preferably, aluminum is used as the matrix material Triisobutylaluminum (hereinafter referred to as TIBA) deposited is, and as reinforcement fiber a carbon fiber,

In the following, exemplary embodiments of the invention are described with reference to the drawing! in this show;

1 shows a schematic view of an apparatus for production of coated fiber according to one embodiment of the invention in batch or batch operations; -. '.

FIG. 2 shows, in a schematic view of the type of FIG. 1, an apparatus for continuous wrapping or sheathing, the fiber; -. "'- ■■

3 shows a side view of a reaction chamber for winding a thread or a fiber with simultaneous covering or sheathing of the fiber;

FIG. 4 is a front view of the apparatus of FIG. 3.

The arrangement shown in Fig. 1 has a reaction vessel 10,

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which in this pall consists of a copper tube furnace heated by heating windings 11. In operation, the furnace 10 is loaded with carbon fibers; the fibers are not heated directly, but rather by heat transfer from the walls of the chamber 10 in such a way that at least the outer parts of the fiber bundle are sufficiently heated. Triisobutyl aluminum is fed to the furnace to produce a sheath or a coating on the fibers heated in this way. It is supplied from a tightly closed bottle 12 which contains TIBA in liquid form. The liquid is extremely dangerous because it burns when it comes into contact with the skin] To avoid manual handling of the liquid, a pressure delivery system is provided for the TIBA. For this purpose, an argon cylinder 13 with a pressure reducing valve Ik and a flow regulator 15 for supplying argon via a line 16 into the bottle 12 is provided. As a result, the contents of the bottle are pressurized and the TIBA is pressed through a further line 17 into a float chamber 18 in which a constant column of liquid is maintained.

The liquid drips from the float chamber 18 through a line 19 and a control valve 12 into an evaporator chamber IJ>, in which it falls onto an electrically heated hot spot and therefore evaporates. A stream of preheated argon and isobutylene is fed into the evaporation chamber 13 as a carrier for the TIBA and to achieve some control of the deposition process. The isobutylene, which is one of the by-products of the deposition reaction, slows down the reaction in such a way that the rate of the reaction can be controlled by adjusting its concentration.

This gas mixture is supplied from an argon cylinder ■■ - ■■ "■■ '■."^; ■ ■■■ V -: -,: ■■; ■■ ^:. ■■ -_ ■■ - ■ - ■ '■■■■., - - ./.

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and an isobutylene cylinder 21 via pressure reducing valves 22, flow regulators 23 and flow measuring devices 2 * »-. In the special The described design of the apparatus was provided in the argon supply line for the argon-oxygen separator Case that the argon supply contains external oxygen. This oxygen separator consists of a furnace in which titanium chips were heated such that any oxygen present combines with the titanium. Previous attempts have shown that this is practically not essential is.

The supplied isobutylene and argon are combined in a line O and pass through a preheating furnace 27, in the form ejnes elongate furnace in which the gas mixture to near ditt required for deposition of the TIBA temperature is erhitist., Nor required to in the reaction chamber 10 To reduce excessive heating.

preheated

The gas mixture flows out of the preheating furnace 27 via a

ffia: r; ejie Äotu.lei üung 28 into the vaporization chamber \ J> _S where it mixes with a vaporized TIBA and flows through a further side line 29 into the reaction chamber 10.

In a 4-way reaction chamber, the close to the wall of the Chamber hewn fibers to a temperature of approximately 2bO ° ■ '"; heated. At this temperature the TIBA decomposes forming, together with hydrogen, gaseous isobutylene and an aluminum deposit which is deposited on the hot surfaces of the fibers. The underlying chemical reaction is as follows:.

(Gas) Al (G ₄ H ₉ J ₅ ²⁶ °° ^C Al (solid) + H ₂ (gas) + C ₄ H ₈

A coating of aluminum is therefore deposited on the fibers.

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The waste products are from the reaction vessel 10 via a Line 30 into a cryogenic condenser 31 and from there into one oil trap 32 discharged. The condenser and the oil trap are for Preparation and, if necessary, recovery of waste products before the "' The remaining exhaust gas is intended to be released into the atmosphere. '

It has been found that, according to the above-described process, carbon fiber can readily be used in batches or batches can be coated} however has this embodiment the main disadvantage of the method that only those adjacent to the surface of the furnace 10 or with it in Contact standing lines are covered, as only these lines are sufficiently heated. According to an improved embodiment the invention is therefore provided in the apparatus the reaction vessel 10 made of a radiation-permeable material manufacture and the fiber material by radiant heat from to be heated outside the reaction vessel. Pig. 2 illustrates this modification in application to a process for continuous coating bsw. Sheathing a Fiber or a fiber bundle.

In the device shown in FIG. 2, exactly the same system is used as in FIG. 1 for supplying the TIBA with the preheated carrier gas from the evaporation chamber 13 via the jacketed pipe 29; this part of the device is therefore not described in detail. The reaction vessel, however, has a significantly different design. In this case, the reaction vessel consists of a glass tube 35 with a tubular inlet end 36 and a tubular outlet end 37.To hold back the gas in the vessel, the supply tube 36 and the outlet tube 37 are gas-tight "Thus, the feed tube is provided driving circuit with a lateral Za ^ 36 provided 38 a with preheated from Argentine

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(not shown) furnace is fed, as well as a second lateral outlet line 39, through which both the preheated Argon from tube 38 as well as the exhaust gases from furnace 35 exit yourself. The outlet line 39 is with outlet traps of the same type as shown at 31 and 32 in Fig. 1, tied together.

A corresponding gas seal is in the outlet line 37 provided, which also serves as an inlet or supply line for the gases from the evaporation chamber 13. the Gas seal has a side branch line 40 which is again fed with preheated argon from the furnace (not shown) «This gas simply flows through the open End of tube 37 to the atmosphere. It can be seen that the gas seals described in the inlet and. the outlet pipe cause a gas flow that opposes any leakage flow from the reaction vessel 35, and therefore carries any leakage out of the reaction vessel *

¹ Since the tubes 36 and 37 are open at their ends, carbon fiber can be continuously fed into and out of the reaction vessel 35, in the specific example shown, a strand bundle of carbon fibers is wound on a feed drum 4i; these are fed in via the inlet tube 36 and via a spreader bar 42 for spreading out the fibers. Such spreader b2w. Distribution rods are known in textile technology and normally consist of a rod lying transversely to the direction of the grain and curved convexly when viewed from above. In this way, the fiber material is spread out into a thin sheet of film as it travels through the glass reaction vessel, as in 4? indicated. Heat radiation sources 44 are provided for heating the fibers during their residence time in the Reatcfelonsgefäß 35. For this purpose, infrared rays can be used

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Alignment are used that its radiant energy falls on the fiber web 47 and increases its temperature. To the can further focus the heat radiation on the faeern Reflectors of elliptical cross-section provided aän.

The radiant heating devices are chosen so that they * a temperature of about 260 ° C in the carbon fiber web generate * One recognizes that by the countercurrent movement of the gas flow and the, fiber web and the high temperature of the Fibers the gas to decompose and form an aluminum layer is caused on the fibers.

The coated or enveloped fiber material finally arrives, still in web form, at the end of the reaction vessel 35 "where it is combined into a bundle by a device 4". This bundle of coated fibers then passes through the outlet tube yj and is wound up on a winding drum 44. In this way, a continuous supply of coated or sheathed fiber is obtained.

The Figg. 3 and 4 show different views of one and the same apparatus for producing an object wound from thread-like or fibrous material, the matrix material of which is simultaneously applied according to the method according to the invention. The details of the TIBA gas generating system are not shown since, as shown in FIGS. 1 and 2. However, in this embodiment, the preheated argon-TIBA mixture obtained as a product of the gas generation system is introduced into a reaction chamber 46 via a nozzle 45. Fiber material can be fed from a drum 48 through the chamber via an input line 47; The V line 47 has a gas seal at 49 which, as in the example described above, is fed with preheated argon.
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In the interior of the reaction chamber 46, a mandrel 50 is in the form a molding block made of a good conductor material such as Copper, provided. The mandrel 50 is by means of a spindle 51 rotatably arranged, which through an opening in the side wall the chamber 46 via a sliding and rotating seal 52 is introduced. The spindle 51 is from outside the chamber 46 driven by a motor 53 and is also by means of Devices not shown in the sense of an axial displacement of the mandrel actuatable.

A heating element stand 54 is arranged within the mandrel 50. The heating device 54 is attached to a seal 55, for example a PTFE (= Teflon) flat seal, which in turn is attached to the wall of the chamber, the attachment the seal the electrical leads for the Heating resistor 54 picks up.

In operation, this system works like. follows: "First the fiber material is wound onto the mandrel 50, then the gas supply is opened through the nozzle 45 and the mandrel 50 is rotated. At the same time, the mandrel 50 is heated by the heating device 54 to a temperature of about 260 ° C. It can be seen that that the fiber material is wound on the mandrel 50 in this way and at the same time is taking place, the deposition process described above to the wound fiber material. ₀ by a transverse movement of the mandrel 50 in the axial direction of winding layers can be of the fiber material be prepared in a known manner.

By having the resistance heating device 54 inside the mandrel 50, the best possible flow is obtained Direction for the separation process; the deposition begins here on the surface of the thorn and sits near the outside through the fibers.

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Furthermore, the heat capacity of the mandrel is chosen to be so large that that temperature fluctuations at the pasers are as small as possible being held.

As an alternative to the arrangement shown, the feed tube 47, through which the fiber material is fed, can be arranged so that they can be pushed back and forth in the transverse direction.

The device described enables the production of wound articles made of composite material, in which the one-piece matrix is simultaneously used with the winding-P Process is established.

The invention has been described above with reference to certain materials described; of course, however, it is also suitable for use in conjunction with other fiber materials and other matrix materials. For example, nickel, cobalt, iron and titanium can all be made from an organometallic Steam or other suitable steam in a similar manner to how described above ,, are deposited for cladding, although in some cases significantly higher temperatures are required.

The based on Fig. 5 and 4 described apparatus could can also be used for the continuous treatment of fiber material; for example, it could be provided that the fiber passed once around the mandrel, then removed and is wound up. ■ "..- ■.

Obviously, other types of heating for the fiber material can also be used; for example, resistance heating could be provided by means of current conducted through the fiber, or the fiber could be heated by microwaves. ~ · _

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Claims (10)

ίί. Pat ant ans pr Uche 1. Process for the production of a with a casing or a coating or sheathing provided Paser, thereby g e k e η η ζ e i c h η e t that the fiber heated and brings a decomposable, metal-containing vapor into contact with the surface of the fiber, wherein the The temperature of the fiber is chosen so that the steam itself on their surface with the formation of a metal deposit decomposed. 2. The method according to claim 1, characterized in that g e k.e η η, ζ e ic h ■ "-. η e t that as a decomposable vapor a vapor is a organometallic compound is used » 3. The method according to claim 2, characterized in that g e k e η η ζ e i oh net, that as a decomposable vapor vaporous TrI-isobutyl-aluminum (TlBA) is used. 4. The method according to one or more of the preceding claims, characterized in that the The fiber is heated by conduction from a hot wall to the fiber. 5 »Method according to claim 4, characterized in that η ζ β loh ·» net that the wall is heated by electrical resistance heating. 6. The method according to one or more of claims 1 to 3, characterized geke η nz ei cha et that the heating of the fiber material occurs duroh radiant heat directed to the fiber. 009808/16 6 0 7. The method according to claim 6, characterized ge k e η η ζ ei c h η e t that the decomposing vapor and the Paser in one Bring the furnace to the effect of animals and the radiant heat through the furnace wall, which is permeable to the heat radiation is fed. · Method according to one or more of the preceding claims in continuous execution, characterized in that one continuously coherent fiber or a fiber strand through a Furnace conducts, in which the decomposition and deposition he follows. 9. The method according to claim 8, characterized in g e k ennzeichn e t, that the fiber is wound up in the furnace to produce an article, such that in the furnace the deposition and the winding take place simultaneously with the production of a continuous, coherent one Matrix body in which the fiber winding is embedded as reinforcement. 10. The method according to one or more of the preceding claims, characterized in that e η η ζ e i c h η e t that a carbon fiber is used as the fiber material. .009808 / 1660 bath