JPS63190078A - Copper coated fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to tows or bundles of copper-coated fibers, methods of making such tows, and composites made from tows of such fibers.6 The coated fibers of the present invention include: Can be used in a number of ways. These tows or fibers are cut and, for example, radar jamming strips (r
adar obscuration chaff)
Can be used as The tow can also be incorporated into the composite with various matrices. Composites using concentrated fibers can have the advantages of copper, such as high electrical and thermal conductivity, and overcome some of the disadvantageous properties of copper, such as high density and high coefficient of thermal expansion. can do.

Prior art describes metal-coated fibers and composites made therefrom, for example, commonly assigned U.S. Patent Application No. 650,583 to Marin.
(filed December 12, 1984 and now patented) describe thin, uniform, tightly bonded conductive layers of metals such as nickel and copper. Morin, U.S. Patent Application No. 507,
No. 603 (filed June 24, 1986 and now patented), their use in metal composites is described. 'Iwasko
w) and Crum, U.S. Patent Application No. 358
．． No. 549 (filed March 16, 1982), their use in polymer composites is described. Marin's US Patent No. 6
No. 3-0.709, filed July 13, 1984 and now patented, their use in radar reflectors is described. Luxon
), US Patent Application No. 869,518 (filed June 2, 1986), describes their use in elongated injection molding granules. However, although such coatings are uniform, tightly adherent, and conductive, they are relatively thin, with thicknesses ranging from 0.25 to
1.0 micron, more usually around 0.5 micron.

As such, they are not useful as starting materials for certain applications, especially direct assembly into composites.

It would be desirable to produce such fibers that are uniform and somewhat relatively thicker.

However, other prior art describes thicker coatings, but excellent uniformity of coating thickness around the circumference of the fibers, from fiber to fiber through the tow, or along the length of the tow. does not have Some prior art materials have highly coated fibers on the outside of the tow, but the inner fibers remain uncoated. Other prior art materials contain fibers plated together in groups, leaving a copper deficiency inside each aggregate.

In general, such surfaces have drawbacks because they impart non-uniform or irregular properties to the materials made from them. In particular, when copper-coated fibers are formed into a copper matrix composite by heating and coalescence under conditions, the lack of uniformity in coating thickness results in an irregular distribution of substrate #l fibers through the resulting copper matrix. will occur,
The presence of aggregates of uncoated fibers and asp creates voids in the matrix in such composites. Such non-uniform distribution of fibers and voids reduces mechanical properties and causes non-uniform thermal or electrical conductivity. Fiber agglomerates may also make it difficult to unroll the fiber tow, thereby making thin composites difficult to manufacture. Furthermore, the presence of aggregates can reduce the flexibility of the fiber tow, thus making it difficult to produce filamentary woven or nonwoven materials.

Among the prior art proposals for producing copper-coated fibers, especially copper-coated carbon fibers, electroplating, electroless plating, electroless plating and subsequent electroplating, bonding (cessenta
tion) and ion plating have all been tried.

Regarding electrolytic deposition, B, W, Hoofe
tt) et al.
roceedins of interna
tional conference ora
Naized b The Plastics
1 institute), Unwin Bros, y Ltd
), Surrey, February 1971,
99-106 Beno] was [to continuously electrodeposit...copper...onto a tow containing 1000 fibers.
A very satisfactory method has been developed." The method is only described as electrolytic deposition via [experimentally formulated solutions of cyanate]. However, photographs of their fibers show highly uneven thickness from fiber to fiber as well as around the circumference of the fiber. In general, this document teaches that direct electrolytic deposition of copper gives a rough, non-uniform coating. For example, M% Sakaki et al., 89.1979, sulfur R copper (20
0 g/l) and sulfuric acid (60 g/l), very severe peaks and valleys were found on the surface of electrostabilized copper. As the attached photo shows, the coating thickness varies equally well from fiber to fiber.
Japanese Patent Open Channel No. 1985-17-095 states that in carbon fiber tow plated from a copper sulfate plating bath, ``due to the roughness of the copper plating layer, soldering ability is poor, found that it was difficult to manufacture.

This patent covers a commercially produced brightener, UBAC-1
, and reported that soldering performance is improved when chloride ions are added to the plating solution. However, no mention is made of the structure of the coating, and as shown in the comparative example below, when iterated therein, inadequate coatings were obtained.

Regarding electroless deposition, several researchers have reported attempts to coat carbon fibers with copper using electroless copper plating methods. Some reports are vague and poorly detailed, such as U.S. Pat. No. 13,550,247, which states that large bundles of fibers can be substantially uniformly coated with metal, No specific method of plating N, C, W, Judd
[! LiL! A report by J. iL, December 1970, page 345, used a proprietary electroless solution to deposit copper onto carbon M&fibers, but an inferior coating was obtained. . ``Fiber coverage in the center of the tow was not achieved.'' Other reports used electroless plating to coat carbon fibers with copper. V,
N., Sakovich et al. [Fiz, K
him, 0brab, Master, (
2) 112-115 (1975)] precipitated copper by treating aJ& surfaces with boiling water, a solution of stannous chloride, and a solution of stannous palladium chloride. Then, "a number of electrolytes were tested using formaldehyde solution as the reducing agent."

They report that [a glossy coating of uniform thickness on all fibers of the tow was obtained from the following electrolytes: A: 170. /l Seignet) (
Salt (potassium sodium tartrate), 50 g/l sodium hydroxide, 30 g/l sodium carbonate; B: 40 percent formaldehyde solution; B: 5: 1 (pH 12°3, temperature 20°C)
”. [The average settling rate of the coating is 0.6 cfm2
The discharge density of the electrolyte of /I was reported to be 0.03 microns/min.

When repeated here, the resulting coating was inferior as shown. German Patent No. 2,658°234 discloses that ``the individual fibers of the bundle are coated and the bundle is exposed to a reaction solution from which a substance is extracted by electrical currentless chemical means. Describes a method for depositing on fibers. To ensure the individualization of the fibers of the tow, [a section of the fiber bundle is loosely suspended and...the reaction is applied along this section, [because of the spreading of the fibers, the reaction solution covers all the fibers. can reach the surface of The fiber is thus
They can be coated uniformly over their length and their cross-section." However, when repeated here, an inadequate coating was produced, as shown in the comparative example.

Regarding the cementation method, B, C
.

Pai et al. [Journal of Science, Letters J ornal or
60-1863 (1980)] reported the use of a bonding method to deposit copper and other metals onto carbon fibers. Nickel and cobalt coated the fibers uniformly, but
It was disclosed that ``copper coating occurs by crosslinking . . . an isolated precipitate.'' Figures 3-7 of this reference show irregularly thick copper coatings.

When it comes to ion plating or vacuum deposition, the prior art
Discloses using ion plating or vacuum deposition to form "an assembly...of a plurality of carbon fibers, each coated with a matrix layer of metal, where the fibers have attachment points to the metal layer". This method does not form individualized fibers. Japanese Patent Disclosure No. 1982-1982-
No. 57.851 discloses the use of ion plating to coat carbon fiber fabric.

However, the goal of this method is not to form individualized fibers, as the present invention requires.

Regarding electroless deposition and subsequent electrolytic deposition, A, M,
Kuz' win et al. [Soviet (U.S.
SR) Patent No. 489,585 and Fiz.

Khi@, 0brab, Mast
er, , 1 9 7 5 (5) 101-1
[06] reported a copper-coated carbon fiber tow produced by depositing a layer of copper using an electroless method followed by further electrolytic deposition of copper. This method consists of materials in which "the fibers of all the elements were covered with a uniform layer of metal in the process of chemical precipitation...the filling of metal between the electrolytic formations of the layers also proceeded uniformly". It is stated that this method gives However, here again, a uniform layer was not obtained. U.S. Patent No. 3,495,940 states [(1) Yes? j! forming a thin film that sensitizes and activates the metal on the surface of the fiber, (2) electrolessly plating a thin layer of copper on the activated surface, and (3) depositing an additional layer of copper on the activated surface. Discloses Method J, which includes the step of electrolytically depositing copper. Using this method,
A copper coating was formed comprising 10-50% by weight of the organic fibers. This is only 0.048 for a 1f14a fiber with a density of 1.25 g/fiber'.
The ~0.24 micron coating thickness is too thin to provide the benefits of the relatively thick copper coating required here. The patentee also used this fiber to electrically heat organic fibers to the point where the fibers carbonized and graphitized to become carbon fibers.

Such methods reduce the volume of the base fibers so that the carbon fibers do not adhere to the metal coating. There is no discussion as to how to handle the fiber tow. Japanese Patent Publication No. 1984-59 Showa-54640 discloses "compound plating that is a combination of electroless plating and electrolytic plating". In this method, carbon fibers are held under tension on a frame and then coated.

The purpose of this method is to prepare copper and carbon fiber [prepreg]
prepreg) J and not individualized coated fibers. Composites produced by hot pressing of prepreg were unsuitable because they had an uneven distribution of fibers, as evidenced by the cross-sectional photographs presented here. The Kuz'win et al. article cited above used a method of air oxidation or nitric acid etching, followed by electroless plating and then electrolytic plating. Although the bath components are listed, the specific formulation is not, and furthermore, the fiber handling techniques are not described. European Patent Publication (EPO) No. and subsequent electrolytic plating to coat a single optical fiber. "In a preferred embodiment...the fibers...are sequentially electrolessly plated in a first step and successively electroplated with a metal layer in a second step...the fibers are subjected to alternating rinsing baths. Pass through a certain number of precipitation baths sequentially...
In a particularly advantageous embodiment, the layer of metal is formed successively by electrodeposition on the electrically conductive layer in at least two successive steps, where between the successive steps the current density is increased and the layer of metal is electrically contact fibers coated with
. Copper plating is not actually illustrated.

Fiber-reinforced composites have also been disclosed in the prior art, and these composites have been formed by a number of techniques. For example, a tow of reinforcing fibers can be impregnated with a slurry of copper powder and then consolidated under heat and pressure. Sometimes this method can include sandwiching the fiber between copper foils. However, such a method has several advantages. Since tI4 does not spontaneously wet some fibers, especially carbon fibers, additives, e.g.
Titanium must be fed into the steel to enable wetting. However, such additives reduce the thermal and electrical conductivity of pure copper. Such composites also have non-uniformly distributed reinforcing fibers.

In order to avoid having to wet the carbon fibers with liquid copper, it is advantageous to coat the carbon fibers individually with copper and to unite the coated fibers under heat and pressure. This general procedure has been used by a number of researchers. However, the ability to uniformly coat all of the tow's fibers has been limited;
Until the present invention, it has not been possible to achieve a uniform distribution of reinforcing fibers in a copper matrix composite. Additionally, it is not unusual to perform heat pressing at very high temperatures (around 900°C), which can cause dewetting of the copper coating from the carbon fibers and lead to defects at the copper/fiber interface. There is.

One object of the present invention is to provide a tow of fibers uniformly coated with copper that is useful as filler or as reinforcing fibers in composites requiring high thermal or electrical conductivity. be. Such fiber tows can be used as free J fibers (as compared to fibers embedded in a composite).

For example, the fibers can be cut and used as radar jamming strips, or used as conductive brushes.

Another object of the invention is to provide a method by which fibers can be uniformly coated with copper.

Another object of the present invention is to provide a copper matrix composite useful as a material for low density lanophytes, low thermal expansion conductors, and other applications.

According to one aspect of the invention, it has a semi-metallic core and at least one relatively thick, uniform, tightly bonded, electrically conductive layer of copper present on said core. , a continuous thread or tow of composite fibers is provided.

According to another aspect of the invention, such a composite fiber tow is prepared by: (1) immersing at least a portion of said length of II & miscellaneous in a bath consisting of a wetting agent in an aqueous medium; (3) sensitizing the surface of the fibers to electroless deposition of metals consisting of copper by immersion in a colloidal suspension bath of chloride of tin; (3) electroless plating of said fibers with metals consisting of copper; (4) immersing the fiber in a bath capable of electrolytically depositing a metal comprising copper; and (5) depositing a conductive layer of metal on the fiber. An external voltage sufficient to deposit copper metal onto the fibers is applied, and the voltage and resulting current are applied to deposit a relatively thick, uniform, hard-bonded coating of copper on the core. Manufactured by holding for a sufficient period of time to produce. These steps must be carried out under low tension and while spreading the fibers.

Such fibers can be used as "free" fibers or, in accordance with yet another aspect of the invention, a continuous thread or tow of composite fibers, said thread or tow comprising a semi-metallic core and said core. at least one relatively thick, uniformly and tightly adhered electrically conductive layer of copper, and a matrix of a metallic or organic polymeric material, the fibers being disposed within the matrix. It can be formed into a complex characterized by: These matrices can be formed by admixture, by direct consolidation by heat pressing, or by other methods.

In accordance with yet another aspect of the invention, an injection molding compound can be produced that is comprised of elongated particles. Each of the granules contains a bundle of elongated composite fibers, the composite fibers having a semi-metallic core and at least one relatively thick, uniform, tightly bonded conductive layer of copper over the core. and wherein the fibers extend substantially parallel to each other in the longitudinal direction of the granules and are substantially uniformly distributed throughout the granules in a thermally stable film-forming thermoplastic adhesive. Dispersed.

Regarding the first two aspects of the invention, the fundamental improvement of the invention over the prior art is that the copper-clad 12,000 (1
2K) One aspect of the present invention is to provide a tow of fibers containing as many as 2K) fibers in which the copper coating is very evenly distributed over the fibers of the tow.

The fibers of the present invention are greater than about 0.5 microns to about 3.0 microns, preferably about 0.6 microns to about 3.0 microns, particularly preferably at least about 0.8 microns, and most preferably about 1 micron. It is possible to have a copper coating thickness greater than .2 microns. The thickness of the coating is uniform around the circumference of the fiber, with an average thickness of 3
It has a standard deviation in thickness not greater than 0%. It is also uniform from fiber to fiber and has a standard deviation in thickness of less than 30% of the average thickness.

Furthermore, in the present invention, the fibers have a low degree of agglomeration.
Typically 80% of the fibers in the tow are present as individually coated fibers. As a result of the low agglomeration in the tow of the fibers of the present invention, the tow is flexible and smooth. Furthermore, the copper coating of the present invention can be very pure. This means that it is possible to obtain the highest thermal and electrical conductivity.

The base fiber of the present invention includes carbon, graphite, polymer,
Including glass or ceramic fibers. The choice of base fiber will depend on the nature of the intended use for the coated fiber. structural carbon fiber with a modulus in the range of 30 to 50 x 10s bonds per square inch (psi);
For example, polyacrylonitrile (PAN) is manufactured from graphite fibers, e.g. pitch, with a modulus of 55-140X10'psi, which would be selected for applications requiring moderate strain versus failure in composites. The prepared fibers could be used where very high thermal or electrical conductivity or very low thermal cohesion is required. Ceramic fibers with large diameters could be used in applications where compressive strength is required. Other criteria will be apparent for analogous composite material designs.

The method of the invention, as diagrammatically shown in FIG.
It has several new and useful properties.

The method of the present invention uses common formulations for electroless baths, but incorporates favorable features that provide stability, plating speed and uniformity of coating on individual fibers through the tow. The coating method provides a uniform product in a patch or continuous process with excellent manufacturing speed and stability of the solution of ingredients.

The continuous aspect of this method uses a surface designed to apply very little tension to the fiber tow and spread the tow. Damage to the fibers is preferably [straig
ht through) is reduced by using a J design, where the fibers travel in an essentially straight path through the plating line. This is achieved by using very low strain-to-failure fibers, such as pitch-based carbon fibers [e.g., Amoco Inc.
) Ploo and P120 fibers] to withstand the rigors of continuous plating processes.

Preferably, and with reference to FIG. 1, the copper coating method of the present invention includes steps performed in the following order: (i) wetting with an aqueous surfactant, (ii) rinsing, (1ii) tin and palladium. (iv) rinsing; (V) coating with electroless copper; (vii) one or more layers of electrolytic copper in a bath of varying current density. (viii) rinsing; (xi) drying.

Rinsing steps (ii), (iv), (vi) and (viii) are optional.

Regarding step (i), the need for a high deposition rate electroless copper solution requires the use of a reducing bath of formaldehyde. Higher speeds have been obtained with this method, but the tow is inferior to the overall plating, resulting in internal fibers that are not coated. To overcome this, suitable wetting agents can be used on the surface of the carbon to provide better penetration into the tow and adsorption of the catalyst. Examples of suitable wetting agents include Arquacl B-100, Ar5ak Chemicals
) [7 Kuzo Hemi America (Akzo Che
It is a surfactant manufactured by A+ie America, Inc., Chicago J., Illinois. It can be used at concentrations in water from 0.1 to 1.0%, although higher and lower concentrations are possible. When using carbon a miscellaneous for wetting, uniform electroless plating of all the filaments in the tow can be obtained at 120°C. Then, such fibers are subjected to an electrolytic plating bath,
For example, such copper-coated carbon fibers produced by the patch method, which can be easily electroplated in acidic steel plating baths, can be used to create copper matrix composites, as exemplified below. suitable for The electroless solution may also contain other additives. Plus, a sensitizer! ? ll(1ii) can also have improved stability by omitting the commonly used urea. These favorable aspects result in a more stable sensitizer and a high deposition rate electroless bath. In particular, mention may be made of the use of a combination of 2,2'-dipyridyl and mercaptobenzothiazole. This further improves the stability of the electroless bath while maintaining high deposition rates. Such solution solutions can be supplemented with copper sulfate, formaldehyde and NaOH and can be used over several days, which is a substantial advantage.

Although conventional acidic copper electroplating solutions deposit copper onto the electroless copper in step (vii), the deposit is dull or coarse (or tends to oxidize quickly after plating). In Acidic Copper Plating, a picrate copper plating solution is used instead of an acidic copper solution, which produces a brighter deposit, which does not oxidize as rapidly as that from a more ordinary acidic solution. The solution is also
The presence of strong acids in the plating solution has the disadvantage of potentially dissolving the thin electroless copper layer on the fibers.

These difficulties are minimized if the fiber is made into an anode before entering the solution.

In either case, unless attention is paid to the tension in the tow, the plating can be very poor when high tension is applied on the fiber, especially on the central filament of the fiber tow. This is avoided when the fibers have little or no tension. In a preferred embodiment of the continuous coating method, all tension is removed. This will plate all the fibers well.

Further details of preferred methods, both batch and continuous, are provided in the Examples.

Regarding the solution used, the preferred wetting agent bath (bath 1)
is preferably 1 ml of Aqua B-1
00/11 deionized water. Arquat (A rq
uad■) B-100 is a cationic, surface-active, water-soluble bennoalkylammonium chloride. It is a 49% solution of alkyldimethylammonium chloride with alkyl groups derived from fatty acids, and surfactants of typical molecular weights change the surface energy of the fibers so that the fibers are more easily wetted by the aqueous solution. and also enhances the adsorption of tin and palladium used as sensitizers on the fiber surface.

A preferred sensitizing bath (bath 2) consists of the following components: 1 g of P
dCIz 500si 4 dissolved in deionized H20; 3001 HCl - 35% hydrochloric acid, carefully added to the palladium chloride solution with stirring; 5n of 1.5H
CI <, dissolved in 100 ml of 35% HCI acid, then added to the above solution; heated to 80 °C, then added 37.5 g of 5 nCL fresh deionized water to a total volume of 11 , then cooled to room temperature and held for 16 hours.

The catalyst is a mixed system and a commercially available formulation. However, here it is preferred not to use sodium chloride in the sensitizing bath, although commercial catalysts containing large amounts of sodium chloride can be used. A suitable electroless copper bath (bath 3) contains the following ingredients: 19. CuSO4.5H20, dissolved in 750 ml of deionized HtO, then with stirring is added: 31 .6 g EDTA ninatrihum salt, dihydrate (ethylenediaminetetraacetic acid); 21 MBT (mercaptobenzothiazole) solution, 0
．． 5g MBT/if methanol; 16g NaOH,
The copper solution, dissolved in 100 ml of deionized H20, is heated to 45° C. and immediately before use, the following are added: 151 formaldehyde, and water added to 11.

Another suitable, particularly preferred, electroless copper bath (bath 4) consists of the following components: 10 g of CuSO-.5 H2O, dissolved in 750 + 111 deionized H,O, then stirred. while adding: 30 g EDTA disodium salt, dihydrate (ethylenediaminetetraacetic acid); 0.51 MBT (mercaptobenzothiazole) solution, 0.5 g MBT/11 methanol; 21 parts 2.2 '
- Dipyridyl (DP) solution, 2g/100ml of meth/
-L, iog NaOH.

Dissolved in 100 ml deionized H20; water 0
．． Add to 9901; Heat the copper solution to 45° C. and immediately before use add: 1011 formaldehyde; Final time 0 should be 11.3.

In the above electroless copper plating solution, copper sulfate is the source of copper ions, and EDTA salt acts as a chelating agent and DP
and MBT act as stabilizers, and sodium hydroxide keeps the solution at high pHs, e.g. 11.3-12.2
However, formaldehyde will act as a reducing agent at an excellent rate.

A suitable electroplating bath (Bath 5) consists of the following components: UNICHROME Pyrophosphate Steel Plating Process; and make a 10 gallon solution using the following ingredients (M&T Chemicals, Inc., New York, NY): Add the following ingredients in the following order to 5 gallons of deionized water, with stirring: Add with: 0.35 gallons M&T Liquid
C11Xb; 3.3: Ml'ron's M&T 17 Kid C-10
-xb copper pyrophosphate-containing solution, and o, os, y
Ron's ammonium hydroxide, C0P,.

Fill with deionized water to a total volume of 10 gallons.

The bath should be used at 54.5°C and pH 8.3±0.2. If additional gloss is desired, the brightener M&T additive PY 61 H (0.9 ml/I) can be added.

Other suitable vernaculars are described in the literature (Lowenheim).

When using the batch method, it is convenient to use a 102 cm (40 inch) cutting section of the tow and a glass weight 1/2 along this tow.The tow is then placed in a suitable container, e.g. It is lowered into a 1 liter graduated shilling containing the various baths so that the weight rests on the bottom of the shilling. In this way, the fibers in the tow stay aligned.

When using a continuous process for the uniform plating of fibers with copper, it is convenient to operate as follows: Referring to Figure 1, the apparatus for this process is shown. The baths are designed to hold the various solutions and allow the fibers to be processed with each solution without passing them over or under rollers, which would increase the amount of tension on the fibers. This plating method is a line-op site! (
1ine of-sight platiB). Figure @2 shows such a tank, which uses the so-called [-eired] J design. This is because a weir or overflow is created at the outlet of the tank. Using such a bath, the fibers can pass through a series of baths without having to pass around a series of rollers or guides after initial unwinding. It is possible to pass several tows through the device in parallel; for example, eight tows or even more can be plated at once.

For feeding, spools of uncoated fibers (not shown) can be supported on bearings, which provide very little tension to allow unwinding of the a-fibers. The tow of fibers is then passed through eye lefts (not shown) which guide the fibers into the first bath (
Figure 2). As shown in FIG. 1, the first bath contains a wetting agent, such as A rquiat, as shown in FIG.
d■) Contains B-100 at a concentration of 0.1% by volume of the solution in the upper tank. Filtration of the solution is performed by an in-line filter and is highly desirable in order to keep all solutions free of broken fiber accumulation.

The fibers are then passed through an optional rinsing station, desirably containing excess surfactant or [drag-through] which may affect the chemistry of subsequent baths.
rough) Remove J. A suitable rinsing station consists of a table over which the fibers run and a spray of water directed downwards onto the table.

The force of the water spray and subsequent run-off of the edge of the "table" facilitates spreading the ma.

This series of @2 vessels were tested at catalyst temperatures, e.g. palladium chloride in hydrochloric acid solution and palladium chloride in (bath 2), this solution serves to activate the surface of the fibers for the electroless deposition of copper. This bath is circulated through a reservoir to maintain the concentration of each component. #l fibers are again optionally, but preferably, rinsed after leaving this bath.

This rinsing is desirable because the drag-out to the subsequent electroless plating tank is the only way to remove electroless plating. This is because it can severely limit the lifetime and efficiency of the solution.

As shown in FIG. 1, the third bath resides in a long bath and provides sufficient residence darkness for electroless plating. Typically it contains an electroless steel plating solution, such as the solutions given for baths 3 or 5 above.

The bath temperature is maintained in the reservoir from which the solution is pumped, as shown in FIG. 2.The heated solution is then pumped into the inner tank of the dammed tank arrangement. Preferably DH is maintained at 11.3±0.5. According to known techniques, the stability of the bath is increased by aerating the bath by rapid pumping, stirring or sparging with gas dispersion tubes. Rapid solution flow also facilitates solution replenishment near the fibers, increasing the rate of copper deposition. The fibers can again optionally be rinsed as before.

Electrolytic plating is then carried out in a series of dammed vessels, all of suitable length, e.g.
0 inches). A plating line can have a large number of baths, e.g. 2.3.4 or more baths, and these can have different current densities. Eight tows of fiber can be used to operate at a current density of 8 amps. The use of a low current in the first bath allows for the initial deposition of an electrolytically plated layer of copper above the electroless copper. The remaining tanks can be operated at 20-30 amps. This promotes more rapid plating in many of the remaining baths. As explained, spreading the fiber tow in each of these vessels is essential in the uniform plating of the fibers and in avoiding the formation of agglomerates. The agitation of the solution by the vibrations generated from the plating process allows the current to be increased without the evolution of hydrogen or any signs of overvoltage in the plating operation, proving that such agitation results in more efficient plating.

The spreading of the fibers in the electrolytic cell according to the invention can be carried out in a number of ways, for example by ultrasonic vibration, stirring of the solution or by physically spreading the fibers. One preferred method is to physically spread the fibers.

It is particularly preferred to use a beater bar to spread the fibers; a suitable beater bar arrangement is shown in FIG. The "L" shaped rod is vibrated vertically. This stirs the solution, forces fresh t# liquid into the fiber tow, and spreads out the fibers of the tow. The movement of fresh solution into the filaments of tow increases the deposition rate and ensures uniformity of plating. Stationary rods at each end of the bath keep the fibers below the solution and also help hold the fibers spread out as they leave the plating bath. The 12th tow of QM-6 fiber is
By the time it reaches the final plating bath, it can expand to almost 1 inch wide. This spreading keeps the fibers from plating together in adjacent filaments and increases the plating rate by increasing the mass rate of solution into the tow.

After the fibers have been plated to a sufficient volume fraction of copper, the fibers are optionally, but preferably, rinsed in a lead bath and then dried by an air knife, heat gun, or rotating drum dryer. In this case, the heating gun is attached to a heating chamber (not shown).The fibers are then wound onto one spool together with other tows or preferably fiber wine coats [e.g. graphite fiber wine coats, +7- Sonia Corporation (Leeso
nia Corp., South Carolina] (not shown) onto separate spools.

Radar chaffs according to the present invention are manufactured by cutting strands of copper-coated composite fiber, as described above, into lengths designed to efficiently reflect impinging radar waves. Preferably, the fibers are cut to a length of approximately 1/2 the wavelength of the radar frequency for which the radar jamming fragment is intended to be used, or, if very high frequencies are encountered, a full wavelength length. Cut into.

In practice, radar operators can monitor several frequencies, typically in the 2-20 GHz range. In the future, radars may be developed using very high frequencies. One advantage of the radar jammer of the present invention is that it can be adapted to the frequencies of current and possible radars. Therefore, the strategic radar jammer of the present invention has different lengths in the range of a few centimeters and shorter (e.g. 0.01c to 10c so), corresponding to half a wavelength (or a full wavelength) over the entire bandwidth. Although filaments can be included, the range that can be achieved with the radar jamming strips of the present invention is from 100 microns to several 100 microns, depending on the particular application considered. However, if the particular collision frequency to be protected against is known, the radar jammer can be "tuned" by increasing the proportion of dipoles in the radar jammer that reflect that particular frequency. , and more dipoles can be dispersed per unit volume of radar jammer.

Radar jamming strips made in accordance with the present invention are more efficient than previously known radar jamming strip materials due to the continuous coating and high purity.

Additionally, because of the core material, the fibers of the radar jamming strip are much stiffer than prior art materials, which facilitates dispersion. This will cause the dipole length to remain in tune with the intended radar frequency.

The dispersibility of the radar jamming fragments can be enhanced by further processing the fibers before shredding to make the IIJII mutually repellent, or at least non-adhesive. For example, coated a! It is a typical method to change the surface quality of the dipoles of the radar jamming strip by rinsing the coated fibers with 1.1. 1.1-) A solution of oleamide in dichloroethane fl (e.g. about 10 g
/l) provides a hydrophobic and smooth surface and greatly facilitates the dispersion of radar jamming fragments. After sizing, drying and melting, the fibers are lightened and the sized tow is typically pulled through a series of rollers or rods.
Sizing breaks down and separates the fibers that overlap. This is also one means of maintaining fiber parallelism. Other rinsing and sizing, as well as other treatments to facilitate dispersion of radar jamming debris, will be readily apparent to those skilled in the art, and are fully encompassed herein.

When a wide range of reflections is desired, a certain amount of contact of the dipoles of the individual radar jamming strips may be advantageous; the contact of the dipoles of the two radar jamming strips according to the invention is effectively longer. Since it creates a dipole, *m'ed contacts provide larger end dipoles that respond at different frequencies as the radar jammer fragments disperse and the individual dipoles separate. This allows radar jamming fragments to be directed against the radar.
Another way of ``tuning in'' is made possible by the present invention. Additionally, the core fibers, e.g. graphite fibers, are available in various shapes, e.g. The advantage is low bulk density.

The relatively small diameter of the fibers contemplated herein allows for chopping to very short lengths, eg 100 microns, to make them useful for very high frequency radar. Also, wide-width reflections are within the scope of the present invention.

Various types of composites of the present invention can be manufactured using a miscellaneous material with copper footings as described above. One possibility is to incorporate such fibers into polymeric and metallic matrices. This method involves directly uniting the copper-coated fibers of the present invention so that the coating becomes a matrix. Simply, for example, 600℃~900℃
The fibers of the present invention can be consolidated to form a substantially void-free, homogeneous composite by heat pressing in a reducing atmosphere or vacuum at a temperature of 725°C to 750°C, most preferably 725°C to 750°C.

The a-fiber of the present invention can also be used for fiber [lay-up (lay-up)
ng up) J, can be fabricated into composites by direct union. To do this, the fibers are aligned into a single layer tow, which can be held together by a temporary binder or simply by the capillary action of water, if desired. These layers are then stacked by holding them in parallel alignment or by varying the angle between adjacent layers to form a cross-plied laminate. Because the physical properties of the composite and fibers are anisotropic, a range of properties can be achieved by varying the orientation of the various layers of the composite.

Since the coating #ll of the present invention has a few aggregates,
The fiber is very thin, for example 0.076111111 (
It can be spread into plies as thin as 3 mils).

Thin plies are advantageous when constructing large area structures, such as radiator structures. In such applications, the composite should be as thin as possible, yet requires several layers with several orientations to obtain sufficient stiffness in all directions. Therefore, the thinner each ply is, the thinner the final multilayer composite will be. By creating thinner structures, structural weight savings can be realized, which is extremely important in atmospheric and aerospace or transportation applications.

Composites produced by direct aggregation of fibers of the present invention are
It has the advantage that the copper remains in close contact with the open fibers of the hot press. This is possible. This is because the carbon fibers are coated with copper by plating methods and consolidated at relatively low temperatures (eg, 750° C.). This allows for dewetting during the coalescence of the fibers into a composite.
tting) will not occur. The composites of the present invention also have the advantage of having a very uniform distribution of matrix fibers throughout the thickness without undesirable matrix-rich regions. Furthermore, the void content of the composite is low. This is because the coating is uniform and the agglomeration rate of the starting coated fibers is low. In addition, the purity of the copper matrix can be very high, and the very low agglomeration rate of the fibers of the present invention can be achieved by using thin copper matrix catalysts, filament-wound composites, and braided composites. The composites of the present invention have excellent mechanical properties due to their uniformity, and excellent thermal and electrical properties due to the purity of the copper component of the composite.

As the comparative examples show, none of the fibers produced in the closest prior art, despite their description, satisfy the properties of the fibers in the present invention or are similar to those provided in the present invention. Do not manufacture composites that contain

Organic polymeric materials for use as matrices in the composites of the present invention are numerous, and generally any known polymeric material can be utilized. By way of example, known organic polymeric materials useful in the present invention include polyesters, polyethers, polycarbonates, epoxides, phenols, epoxy-novolacs, epoxy-polyurethanes, urea-type resins, Formaldehyde resin, melamine AT fat, melamine thiourea resin, urea-aldehyde resin, alkyd resin, polysulfide resin, vinyl organic prepolymer resin, polyfunctional vinyl ether, cyclic ether, cyclic ester,
polycarbonate co-ester, polycarbonate
co-silicone, polyether ester, polyimide,
Bisimide, polyamide, polyesterimide, polyamideimide, polyetherimide and polyvinyl chloride.

Polymeric materials can be present alone or in combination with copolymers, and blends of compatible polymers can also be used.

Briefly, any common polymeric material may be selected, and the particular polymer chosen is generally not critical to the invention. When combined with composite fibers, polymeric materials can be treated with heat or light alone or in combination with catalysts, promoters, cross-linking agents, etc.
It can be converted to form the components of the present invention.

The conductive composite fiber used in the present invention is shown in FIG.
A cross section of a composite fiber in an epoxy resin matrix is shown. Each composite fiber consists of a core, indicated by a black circle, and at least one relatively thick, uniform core, indicated by a ring, of bonded, electrically and/or thermally conductive copper layers. , graphite, polymer,
Fibers for use as the core material are commercially available from a number of sources, although they can be made from glass, ceramic, or other fibers, with carbon and graphite fibrils or filaments being particularly preferred.

Such composite A-fibers are well suited for incorporation with polymers to form electrically conductive components. Because the composite #l fibers have a very high aspect ratio, i.e., height-to-diameter ratio, close a-spacing contact to provide a conductive path through the matrix of the polymer is essential for relatively low fiber formulations. levels, and more specifically, much lower levels than the metallized spheres and metal 7 rakes utilized in prior art attempts, to provide conductive polymer compositions. This ability to provide electrical and/or thermal conductivity at low concentrations of fibers significantly reduces undesirable degradation or modification of the physical properties of the polymer.

The copper-coated fibers can be present in the composite as a single strand or bundle of fibers or filaments. Fibers or bundles can be woven into fabric or sheets. Additionally, the fibers or bundles can be ground and dispersed within polymeric materials, made into non-woven mats, etc., all according to techniques well known in the art.

The complexes of the invention can be converted into many components.

In one embodiment of the invention, the composite is a composite WL
A coarse nonwoven mat is produced, for example, by immersing and wetting it in a solution of a polymeric resin, such as a solution formed by dissolving an epoxy resin or a phenolic resin in an alcoholic solvent. other forms,
For example, fabrics made of unidirectional fibers, braided fabric foils, and knitted fabric foils can also be used. This composite is then combined with a resin-impregnated prepreg useful for forming conductive laminates. More specifically, the polymer resin solution can be heated to drive out the alcohol solvent.6 Once the solvent removal is complete, the polymer resin layer has a randomly oriented structure. and a component consisting of layers of overlapping composite fibers or bundles of composite fibers is formed, and in this case a layer of epoxy or phenolic resin coats said fibers and fills the voids or interstices within the mat. .

The resin-impregnated prepregs so formed can be cut to standard dimensions and several of the prepregs can be aligned on top of each other to form a layup. The layup is then heated under pressure in conventional lamination equipment where the polymer layers flow and then cure, thereby melting the layers of the layup together to form a cured, unitary laminate. The impregnation, drying, lay-up and bonding steps for making these laminates are conventional and well known in the art.

Further references regarding materials, handling, and processing are found in Encyclopedia of Copolymer Chemistry and Technology (Danfu■卦月±1'')
and Technolo), Vol. 8.
121-162, Interscience, New York, 1969. Laminates made in accordance with the present invention may be cut, formed,
or otherwise shaped into many useful articles. For example, laminates can be made to form the basic base or housing for electrical components or devices, such as motors, and the housing is electrically conductive, thus effectively grounding the device.

In another embodiment, the compositions of the invention are comprised of thin, normally non-conductive polymeric films or sheets, woven, non-woven unidirectional sheets, etc. formed from bicomponent fibers. Polymeric films or sheets can be formed by conventional film forming techniques. Such forming methods, for example, forcing the polymer into a nip formed in the opening of heated rolls of a calendering device;
Alternatively, the polymeric material may be dissolved in a suitable solvent, and then the polymer solution may be coated onto a release sheet, e.g., release kraft paper, e.g. with a "knife-wipe" device, and heated to remove the solvent. Then,
Polymer film or sheet from 37.8 to 93.3
℃ (100-200''F) and laminated with a nonwoven mat of bicomponent fibers by passing the two layers between the heated nips of a calender. The resulting component in film form is useful, for example, as a top ply in a laminate.

Aircraft structures made using such laminates provide an effective lightning shock dissipation system for aircraft. In the past, when lightning struck an aircraft,
Since non-metallic parts are non-conductive, they would have suffered considerable damage. When such a laminate forms the outer surface of the Air 7 Oil, the resulting electrical current is conducted and dissipated through the mat of conductive fibers and the conductive substrate laminate, thereby reducing the occurrence of hazards and damage to the Air 7 Oil. do.

In still other embodiments of the invention, the composite is made from a molding composition, wherein the polymeric material is, for example, polyester, polycarbonate, polystyrene, nylon, etc., and the resin molding composition is made of shredded or It has in contact therewith a crushed copper-coated fiber or non-woven mat. The coated fibers are dispersed in the resin by conventional means and the composition is extruded to form pellets. The pellets are then injection molded according to conventional procedures to produce shaped electrically conductive molded articles. Molded polyester resin articles exhibit excellent physical properties as well as conductivity.

Each of the elongated granules of the present invention contains a bundle of elongated reinforcing copper-coated fibers as defined above, said copper-coated fibers extending substantially parallel to each other in the longitudinal direction of the granule and being thermally stable. substantially uniformly dispersed in a film-forming thermoplastic adhesive comprising: (a) poly(02C@alkyloxazoline) and (b) poly(vinylpyrrolidone). , the adhesive substantially surrounding each filament.

The injection molding composition consists of (i) thermoplastic resin molding granules, and (ii) elongated granules, the elongated granules containing 67.5 to 97.5% by volume of reinforcing copper-coated #l fibers. 12.5 to 32.5% by volume of a heat-stable film-forming adhesive, said copper-coated fibers extending substantially parallel to each other in the longitudinal direction of the granules and comprising a heat-stable film-forming thermoplastic. substantially uniformly dispersed in the adhesive, said adhesive comprising a combination of: (a) poly(cz-cs alkyloxazoline); and (b) poly(vinylpyrrolidone); The amount of component (ii) is 1 to 60 per 100% by weight of (i) + (ii)
% by weight of said filament.

In yet another aspect, the present invention provides an improvement in an injection molding process comprising: (i) thermoplastic molding granules; and (ii) an amount of ll1i elongated granules defined above in an amount effective to provide reinforcement. , into a mold. Each filament contained in the injection molded granules is surrounded by a combination of heat-stable film-forming adhesives and the bundle is impregnated with a combination of heat-stable film-forming adhesives. The pellet itself can be cylindrical or rectangular or have any other cross-sectional shape, but is preferably cylindrical. The length of the grains can vary, but for most of them 0
．． 64-0.75 cm (1/4-374 inch) is acceptable, and 0.32-0.64 cm (1/4-0.64 cm)
/8 to 1/4 inch) would be preferred.

Unlike the prior art, the pellets of the present invention are closely packed filaments and the thermoplastic adhesive jacket is substantially dispersed upon contact with the hot molten thermoplastic material of the present invention. On the other hand, prior art pellets do not easily separate into reinforcing filaments due to interference from the relatively thick jacket of thermoplastic resin.

Instead of using large amounts of resin to impregnate and surround the bundle of fibers, as practiced in the prior art, the use of an adhesive that is efficient for the purposes of the present invention, i.e. It is essential to combine a high proportion of filaments into each elongated granule and maintain them in the chopping process and subsequent compounding steps in high speed, high throughput machines. The adhesive is preferably #lI during shredding
I & in an amount not substantially exceeding that which maintains the integrity of the bundle,
It will also be used. This amount will vary depending on the nature of the fibers, the number of fibers in the bundle, the surface area of the fibers, and the efficacy of the adhesive, but generally 2.5 to 3
It will vary by 2.5% by volume, preferably from 5 to 15% by volume.

For uniform adhesive deposition on the fibers in the bundle, it is preferred to use a small but effective amount of surfactant, which promotes wetting and bonding to a number of different substrates. Anionic, cationic and nonionic surfactants are suitable for this purpose, the only requirements being that they be miscible with the solvent type used for impregnation and in combination with the thermoplastic film-forming adhesive. This means that they are compatible. Preferred surfactants consist of anionic surfactants, especially when graphite or metal-coated carbon fibers are used, especially the sodium salts of furkylsulfonic acid. Particularly useful is sodium heptadecyl sulfate, sold by Union Carbide Company under the trademark NIACET No. 7.

Careful consideration should be given to the selection of film-forming thermoplastic adhesive combinations according to the aforementioned parameters. Some adhesives are more efficient than others, and while some have been suggested for use as fiber sizes in the prior art, some may not be effective.6 For example, poly(vinyl acetate) and (vinyl alcohol)
[The former is BradL U.S. Patent No. 2,87]
1 suggested as a sizing agent in No. 7゜501
Such materials are not effective in the present invention because it is believed that thermal curing or crosslinking occurs and this prevents rapid melt rise and complete dispersion within the injection molding machine. It is suitable for resin-rich blended granules used in the invention, but is unsuitable for the invention.

The combination consisting of poly(C2C@alkyloxazoline) and poly(vinylpyrrolidone) is highly preferred for use in the present invention, the former being more or less structurally N,N-
It is related to dimethylformamide (DMF) and has many of its miscible properties. A readily available such polymer is poly(2-ethyloxazoline), Dow Chemical Company, PEOx. It can also be made by techniques known to those skilled in the art. Poly(2-ethyloxazoline) is a thermoplastic, low viscosity, water-soluble adhesive. It is an amber transparent beret, 0.48 cm (3/16 inch) long and 0.13 cm (178 inch) in diameter.
Typical molecular weight is 50°000 (low): 200,00
0 (medium) and 50o, ooo (high), it is water soluble, so it is environmentally acceptable for deposition from aqueous media. It also wets the fibers well due to its low viscosity. It has a molecular weight of 5oo in air,
ooo and thermally stable at 380°C (680”F)*.

Poly(vinylpyrrolidone) is a commercial product, widely available from a number of sources, and the molecular weight can be varied as desired.

Poly(oxazoline) appears to provide dispersibility to the elongated bundles, and poly(vinylpyrrolidone) is useful for resistance to high temperatures. Similar to the oxazolines, poly(vinylpyrrolidone) works well in aqueous impregnation media; readily available typical molecular weight ranges include, for example, io, ooo; 24,000: 40,000: and 220,000. Can be used. Higher molecular weight materials tend to provide bundles that are more difficult to disperse. On the other hand, the lowest molecular weight results in some loss of heat resistance. However, within the above parameters, the adhesive combination on the fibers does not appreciably fracture during shredding, minimizing the scattering of loose filaments that can be a safety hazard.

When compounded with thermoplastic resin, the adhesive combination will be present in the molding machine and will melt easily.
This would allow complete dispersion of the fibers throughout the resin melt; however, the pellets combined with this thermoplastic adhesive combination would be infinitely stable with the resin pellets during compounding, and would permanently break. Do not separate.

As a result of a number of tests, this aspect of the invention currently performed provides optimal results when the following guidelines are followed: The type of fiber can be varied and used as a filler or reinforcement in resin systems. Any fiber known to be useful can be used. Preferred fibers are carbon or graphite fibers, glass fibers, aramid fibers, ceramic fibers such as alumina or silica carbide fibers,
metal-coated graphite fibers, or any mixture thereof.

The preferred thermoplastic adhesive component (a) is about 25,000
~about i,ooo,ooo, preferably so,ooo~5
00,000 tlAB, most preferably about so, oo
It consists of poly(ethyloxazoline) having a molecular weight of o.

A preferred thermoplastic adhesive component (b) has a molecular weight of about 10°000
~about 220,000, preferably 24. OOO~40,
24,000, most preferably about 24,000.

The adhesive is preferably deposited onto the filament from a solvent system, which can consist of any polar organic solvent, such as methanol, or a mixture of such solvents, or water alone or in a mixture therewith. . Acceptable bath concentrations of thermoplastic adhesives can vary, but generally from 2.5 to 12% by weight, preferably from 2.5 to 8%, particularly preferably from 4 to 8% by weight, for component (a). weight range, and for component (b) 1 to 8 weight percent, preferably 1 to 6 weight percent, particularly preferably 1 to 4 weight percent.
% by weight.

When using surfactants, this can also vary in type and amount, but generally when using anionic alkyl sulfates, such as sodium heptadecyl sulfate, the bath concentration will be between o,ooos and 0. .5
% by weight, preferably from o,oos to 0.05% by weight, most preferably from o,oos to 0.005% by weight.

The amount of materials other than filaments in the filament-containing granules of the present invention will vary, but generally 2.5 to 32.5% by volume, preferably 5 to 15% by volume with any fibers.
It will be in the range of % by volume.

The amount of component (b) will be from about 7.5 to about 75%, preferably from about 15 to about 50% by weight, based on the combined weight of (a) and (b).

The length of the elongated grains is 0.32-1°91cm (1/8~
3/4 inch), preferably 0.32 to 0.64 cm (
1/8-1/4 inch).

The diameter of each elongated grain can vary depending primarily on the number of filaments, and the thickness can range from about 0.053 to
It will vary in diameter from about 1/48 to about 3716 inches. Preferably the diameter is about 0.07
9 - Will range from about 1/32 to about 1/8 inch.

A number of thermoplastic resins can be used with the elongated granules of the present invention. In general, any resin that is injection moldable and that can benefit from uniform dispersion of miscellaneous materials can be used. For example, polystyrene, styrene/acrylic acid copolymer, styrene/acrylonitrile polymer, polycarbonate, poly(notyl methacrylate), poly(acrylonitrile/phtadiene/styrene), polyphenylene ether, nylon, poly(1,4-butylene terephthalate), etc. Any mixture of etc. can be used.

The injection molding compositions of the invention are preferably manufactured by a continuous process; a suitable apparatus is shown in Figure 5a. Typically, a bundle of filaments, such as a tow of graphite fibers or a tow of metallized graphite fibers,
3.000-12°000 filaments/strand, glass yarn, 240 filaments/strand, or stainless steel tow, 1159 filaments/bundle are pulled from the storage roller and thermally stable film formation in a solution-based medium, e.g., water. The filament is impregnated by passing it through one or more baths 4 containing a thermoplastic adhesive and then passed through means, such as a gooey 6, to control the coverage. Thereafter, the impregnated filament is placed in a heating zone, e.g. furnace 8, to evaporate the solvent, e.g. water, and then melt the thermoplastic adhesive. Treated filament 1
0 from the heating zone, transferred to the shredder 12, and illustratively 0.32-0.6 according to specific equipment requirements.
mJII varying from 4c+e (1/8-1/4 inch)
Cut into berets. The pellets are then stored in a suitable container 14 for subsequent use. It is convenient to add any surfactant into a single solution containing the adhesive. This procedure will result in orientation of the reinforcing fibers along one axis of the grain.

In order to carry out the molding method of the present invention, it is preferable to use the general form 70-diagram illustrated in Figure #55b.
8 to form a blended mixture 20. This is added to a conventional hopper 22 on a molded press 24.

Uniform distribution of the i-fibers is achieved by passing them through a Schilling-26 before forcing them into the mold 28. The molded article 30 is removed to provide a fiber reinforced article made in accordance with the present invention.

May contain other plasticizers, mold release agents, colorants, etc.
And it will be appreciated that the amount of toughening agent in the ingredients can be varied according to well-understood techniques in the art.

The invention is illustrated by the following examples. These examples should not be construed as limiting the scope of the claims in any way.

Examples 1-7 The batch process of the present invention was used in the following examples. Various copper coating thicknesses could be produced on the fibers by first electrolessly depositing the copper for a predetermined time and then electrodepositing with various residence times. The carbon fiber used was manufactured by Hercules + Inc.
Unsized, untwisted Magnamite (M agn, U tah) sourced from
Fiber i Le ■) IM-6,12. #l&
The fibers were prepared for coating using Wetting Bath 1 and Sensitizing Bath 2 as described above, and separate samples of the fiber tows were immersed in Electroless Plating Bath 3 for 3 or 5 minutes. These samples were then electroplated using Bath 5 described above for various times as listed in the chart below. The thickness of the Al1 fiber coating was determined and included below.

Electroless deposition Electrolytic deposition Coating thickness 119 -Lt
L--mouth LL Moxibustion work 2 Kue 2 to 1 (vs. 0 5
0 light) 1 1 3 0.932 3
1 0.283 3
3 0.914 3
5 2.635
5 0 0.836
5 3 0.53
7 5 5 2.31
Control Example A lacks a layer of electroless copper and is therefore not electroplated. The coating thickness in Example 6 was unusually low, likely measuring a non-representative fiber.

Example 8 Three graphite fiber tows IM-
6 (12K) was copper coated using baths 1.2.4 and 5 described above at a speed of 7.62 cm (3 inches) and 7 minutes.

The temperature of the electroless bath was 45°C and the temperature of the electrolytic bath was 53°C. The current in the first bath was 5 amps, the current in the second bath was 30 amps, and the current in the last bath was 12.5 amps. coating continuity, thickness and fiber cohesion,
Measurements were made by scanning electron spectroscopy (SEM) of cross-sections of tows embedded and gripped in niboxy according to standard procedures. The results are summarized in the table below.

% agglomerated alpha fibers 26 Coating thickness range 1.4-2.8 microns Coating thickness distribution between 1-2 microns 99% Mono-a miscellaneous % 74 Examples 9 and 10 Batches of the invention The method sequentially coated 12 tows of IM-6 Gra7ite fiber with copper using baths 1.2.4 and 5 as described above. Both tows were held in Bath 4 for 5 minutes. Example 9 was electroplated at 2.5 amps for 5 minutes. Example 10 was electroplated at 2.5 amps for 10 minutes.

An optical micrograph of Example 9 is shown in FIG. ,
SEM analysis of the cross sections of two tows is shown below: Example 9 Uniformity around the circumference: Excellent minimum thickness:
0.5 micron Maximum thickness: 0.81 micron Average thickness: 0.64 micron Standard deviation of thickness (fiber to fiber): 0.08 micron 11: Number of fibers in each aggregate 1234566 of larger fibers % Example 10 Uniformity around the circumference: Excellent minimum thickness:
0,59 micron Maximum thickness: 1,07 micron Average thickness: 0,77 micron Standard deviation of thickness (Jffi fiber vs. fiber s>: o, 1i micron Agglomeration: Number of fibers in each aggregate greater than 1234566 % of Fiber Examples 11 and 12 Copper-coated carbon fibers were prepared according to the continuous process described in Example 8.
Prepared using baths 1.2.4 and 5. Two base fibers were used: 12 IM-6 graphite fibers (Hercules Co, +Magma, U
tah) and P100 graphite fiber fi (U
nion Carbide Co, Danb
uryyCT), the coating was applied to a sufficient thickness to yield approximately 50% copper by volume. The coated fiber tows were then aligned by hand to form a unidirectionally aligned sample 2,54X20,3c+e (IX8 chinch). A hot press, a large hot press (Figure 4)
by heating to 750-775° C. under a pressure of 1000 psi.

Composite panels were measured for electrical resistance, thermal conductivity, and coefficient of thermal expansion. The coefficient of thermal expansion is push rod
rod) Thermal conductivity was measured using the axial rod technique, corrected for 6 radial temperature losses measured according to the coefficient of thermal expansion method. Electrical resistance was measured using a four point bending technique. All measurements were performed parallel to the a-fiber axis. All of the hot pressed samples were well united. A high fiber volume fraction with low void content provides I
Obtained for both M-6 and Ploo carbon fibers. The thickness of the individual plies was 0.05 mm in these samples.
It was as low as 0.013co+ (5 mils). The test results are listed in the table below: 119 11 1L fiber AI / ?
) 'J y 9 X I M 6 / P
100/Copper composite Copper composite electrical resistance (μohm m) 0.05 (j 0.035 Thermal conductivity (Watt/sK) 194 454 Coefficient of thermal expansion (xio-'/'C) 5,00 2.00 These values are based on the rule-of-mix calculation.
ture calculation), demonstrating uniformity, low void content, and high purity coatings.

Example 13 The fibers of Example 8 were made into a short length of 0.32XO, 64 cm (
1/8xl/4 inch), then mixed well with thermoplastic nylon polyamide in an extruder, and the extrudate was shredded into moldable pellets according to conventional procedures.

The size of the pellet is 10゜2cm x 20.3cm x 0.3
Injection molded in 2 cm (4 inches x 8 inches x 1/8 inch) black.

This black was reinforced with copper coated fibers. Thanks to the metal content, it also does not accumulate static charges and ends up acting as an electrical shield in the electronic 7 assembly.

Example 14 Prepared according to the procedure of Example 8, approximately 2°54 cm long.
(1 inch) of copper-plated graphite fibers were mixed with uncoated graphite fibers in a 1:9 ratio and laid up into a non-woven mat at 33.9 g/m" (1 oz/1 square yard). .

This mat has a copper metal content of approximately 10% by weight, is impregnated with a thermosetting resin face, and is consolidated under heat and pressure to provide great strength and very good electrical dissipation properties. It was possible to obtain a reinforced laminate with

Example 15 A long copper-coated graphite thread prepared by the general procedure of Example 8 was pultruded at high speed with molten lead in an apparatus from which a 0.32 fiber (1/8 inch) diameter rod solidified. A reinforced composite with a lead matrix according to the present invention will be obtained, appearing in the form of a lead matrix with copper-coated graphite fibers running through the center of the rod.

Example 16 The following example illustrates the preparation of an epoxy resin film filled with crushed copper-coated graphite fibers as a conductive surface ply for a laminate. 70
Catalyzed epoxy resin system (American Cy7namide FM) dissolved in a 50750 v/v mixture of ethylene dichloride and methyl ethyl ketone at ~80% solids.
@300) solution in a 3.79 liter (1 gallon) capacity Ross Planetary (Ross P Ian
atary) in a mixer. ml according to Example 8 here! 1 and 0. Thirty stacks of copper-coated graphite fibers chopped into 1/64 inch lengths are added to the mixer and the composition is mixed until the copper fibers are evenly distributed throughout.

The composition was degassed by stirring for 15 minutes under a vacuum of 20 mmHH. an epoxy-shredded fiber composition;
Coat a sheet of siliconized kraft paper with a knife over roll to a thickness of approximately 0.03 cm (12 mils).
Drying was carried out by gradual heating to 8°C (below 190°) and this temperature of 88°C (below 19°) was maintained for approximately 40 minutes. A dry filled polymer film according to the invention is produced. A film of the polymer produced above is used as a surface ply to produce a laminate according to standard procedures. This layup contains 12 layers of commercial prepreg, which is bagged and cured in an autoclave at 20-50 psi for 120 minutes at 350'F. The finished laminate has a uniform, smooth surface suitable for end use without the need for further finishing operations. ASTMO25
7-78, the surface ply has a very low surface resistance.

Example 17 The following illustrates the use of the composition of the present invention as a conductive molding compound.

The following reaction components were mixed in a sigma mixer (sigma m1x
Prepare a polyester molding compound by feeding: 10.5 parts of styrenated thermoset polyester resin (U
SS Chemical MR13017); 12.3 parts styrenated thermosetting polyester resin (USS Chemical MR13018); 0.6 parts calcium stearate; 40.3 parts calcium carbonate; 0.5 parts t-butyl perbenzoate; and 0.0671 inhibitor (35% in dibutyl phthalate)
hydroquinone).

After mixing for 15 minutes, copper-plated graphite atomized (Example 8) chopped into 1/4-inch pieces was mixed.
) into the mixture for 10 minutes. The resulting polymer premix was heated at 150° C. in a molding press for 1
Shape into a 0.2c+a (4 inch) round black.

This black has a very low surface resistance due to the content of metallized fibers. Similar to the compositions of Examples 16 and 17, these compositions also have utility for conductive tools for use in molding due to their excellent thermal conductivity. These tools have unique properties that allow them to build up heat and cool down more quickly, resulting in shorter cycles. In contrast, tools made from conventional materials require significantly longer cycle times.

Example 18 A radar jamming strip according to the present invention is made by chopping a strand of metallized composite fiber as described in Example 8 into lengths designed to effectively reflect impinging radar waves. Manufactured by Preferably, the fiber is cut to a length of approximately 1/2 the wavelength of the radar frequency for which it is intended to be used, or, if very high radar frequencies are encountered, cut to the full length of that wave. do. In practice, radar operators can monitor several different frequencies, typically in the 2-20 GHz range. Therefore, a strategic radar jammer according to the invention can be used for half-wavelength (or full-wavelength) over the entire bandwidth.
The range that can be achieved using the radar jamming strip of the invention made to contain filaments of different lengths ranging from a few centimeters and shorter (e.g. 0.01 to 10 cm), corresponding to , from 100 microns to several 100 meters, depending on the particular application considered.

Example 19 Using equipment of the type schematically shown in Figure 5a, a batch consisting of the following ingredients is compounded: Poly(ethyloxazoline), molecular weight 50.000 6.0 Poly(N-vinyl) pyrrolidone), molecular weight 24,000 4.0 sodium heptadecyl sulfate o, ooi% water
89. 899 trademark near seven (
NIACET@) No. 7 Surfactant Referring to Figure 5a, continuous graphite fiber tows 2 [12,000 count], each having a copper coating thereon, are guided through bath 4. Each of the filaments has an average diameter of about 7 microns. The copper coating thereon is approximately 1.5 mm thick.
It is 0 micron. A copper-coated graphite tow is produced by sequential electroless plating followed by electroplating according to the procedure described in Example 8. After passing through bath 4, the treated mash is passed over grooved rollers 6 to remove excess adhesive, and then furnace 8 is heated to 149'C (3
The impregnated filament was then chopped at a chopper 19112 to a length of 0.64 ell (1 x 4 inch) and approximately 0.1 inch in diameter.
6ea+ (1/16 inch) cylindrical elongated granules are produced. Content of materials other than filament is 9% by volume
It is.

EXAMPLE 20 Using the method schematically shown in FIG. 5b, a sufficient amount of the long pellets 16 produced in Example 19 are injected into a thermoplastic molding resin consisting of poly(bis7er/- Δcarbonate). Composition [Mobay Kanha=-(Mobay C
o.) Blend with MERLO No. 65601 pellets 18 to provide 5% by weight copper-coated graphite filaments in blend 20. The compounded mixture is formed in an injection molding press 28 into workpieces 30 suitable for physical and electrical testing. The electromagnetic shielding effectiveness (SE) and EMr attenuation are measured and show high dispersion efficiency.

Example 21 The procedure of Example 20 is repeated, but instead of thermoplastic pellets, poly(acrylonitrile/butanoene/
Pellets made of styrene) resin [Borg-like Warner (
Borg Warner) CYCOLAC@KJB]
to form a black suitable for measuring the SE effect.

Example 22 The procedure of Example 20 is repeated, but with Bo1j (2,6-nomethyl-1,4-7!nylene ether)-high impact rubber modified polystyrene resin pellets [General Electric NORY
L@N-190] is used instead and a black suitable for measuring the SE effect is produced.

Examples 23 and 24 The general procedure of Examples 9 and 10 was repeated using IM-6 for Example 23 and P-55 for Example 24. IM-6 fibers were coated to contain 50% copper by volume and P-55ai was coated to contain 40% copper by volume. Each fiber was heated at 900°C under Par 7 with 3% hydrogen gas and 97% nitrogen gas.
, for 10 minutes at 1000 psi. Figure 18 shows [cross-plied
Optical micrograph of a 50 vol.% copper coated M-6 bonded into a J laminate in which the fibers in the central layer lie at an angle of approximately 60° to the polished plane. However, in the top and bottom layers, the fibers lie perpendicular to the polished plane. 1st
Figure 7 is a higher magnification photograph of approximately 40% copper coated P-55. In this laminate, all fibers shown are oriented perpendicular to the polished plane.

For comparison purposes, a number of copper-plated graphite fibers are produced by prior art techniques and compared to those produced in accordance with the present invention.

Comparative Example IA Direct electroplating of green tow of graphite fibers
An attempt was made to use a commercially available copper electroplating ectotherm.

The plating solution used was Yu-5 described above. The graphite fiber used was Plo from Union Carbide.
o (2,000 filaments, no size, no twist)
Met. The graphite fibers were believed to have sufficient electrical conductivity to allow electrodeposition of copper. A 1 liter graduated cylinder was filled with 1 liter of bath 5.

The bath is heated by heating tape wrapped around the cylinder.
Heated to 5°C. The tape was connected to a variable voltage controller and then monitored by a thermometer suspended inside the cylinder. Two rectangular 0FHC grade copper sheet blanks (high purity copper) were suspended in the bath by bending one end of the sheet over the side of the cylinder. These sheets were connected to a power supply to act as cathodes. The pioo@fiber is wrapped around a piece of copper rod material that is stationary at the top of the scale.
The fiber was fastened to a rod and connected as an anode to a power supply. Plating was carried out for 5 minutes using a current of 1 amp. The fibers were then rinsed with deionized water and
1 at 48.9°C (120″F) in a vacuum of wmHH
Dry in a vacuum oven for 5 minutes. Visual inspection of the fibers showed that the plating was sporadic and non-uniform. This material was considered unsuitable for hot pressing.

Comparative Example 2A The sizing agent was commercially available graphite fiber (2
,000 filaments, untwisted, unsized) by heating to 400° C. for 30 seconds in air using the procedure specified by the fiber manufacturer, Union Carbide. Zero-order solutions were used with 1 liter of each solution in a graduated cylinder: Bath 1
was the previously described wetting agent solution at room temperature, Bath 2 was the previously described catalyst f# solution at room temperature, and Bath 3 was the previously described electroless copper plating solution at 45°C. The final bath was vented by a gas dispersion tube connected to a compressed air line.

6 bundles of fiber, each 6.35 cm (2.5 inches) long
, was soaked in Yu-1 for 2 minutes, agitated by hand, and rinsed with deionized water. The fibers were then stirred in bath 2 for 2 minutes and rinsed again.Rinsing continued until the effluent from the fibers was clear and colorless.The individual bundles were then placed in bath 3.
1.5, 10.15 and 30 minutes separately. I tried plating 6 F pieces for 1 hour, but
The plating bath became unstable, began to precipitate, and the experiment was stopped.6 The fibers were then dried in a vacuum oven. The resulting fibers were mounted in a scanning electron microscope (SEM) and the coating thickness was measured. Thicknesses ranged from 0.3 microns at a 1 minute residence time to 3.0 microns at a 30 minute residence time. Coating is carried out in plating solution at 1
After 0 minutes, it was observed that the nodes began to grow.6
At 10 minutes, the coating thickness was 1.8 microns.

Comparative Example 3A The method described in German Patent No. 2.658,234 is said to ensure a uniform coating of individual very thin abrasives with a coating of metal, for example copper. This patent diagrammatically shows an apparatus consisting of a funnel suspending a graphite tow. Various solutions are then pumped into the funnel, which flows down the tow and spreads it out. The main requirements of this device are as follows: a pump, capable of achieving a flow of 1 liter / minute, and a funnel, with an inner diameter of 3 to 12 times the outer diameter of the tow to be coated. The height of the liquid in the funnel is 2
The advantage of this particular method lies in the fact that the individual fibers spread out from each other in the flow of the reaction fluid flowing along the individual fibers. teaches that the flow rate along the length will produce fibers that will be coated uniformly over both the length and the cross-section. Detailed instructions are given for the pumping time and water rinsing for each component. Unfortunately, German Patent No. 2,658.234 Commercial electroless plating solution used in Sibley Co., Ltd. (Ship
ley company) is no longer available. A diagram of this device is given in FIG. The solution was pumped into a plastic funnel using a magnetically driven plastic pump (Teel). Pump flow was restricted by a W4rII capable hose clamp.

The flow was adjusted to 1 liter/min. The inner diameter of the opening at the bottom of the funnel was 0.5 cm. Using a pumping speed of 1 liter/min and this funnel, when the fiber tow was suspended through the opening of the funnel, the liquid level of the solution in the funnel could be maintained at 5 ca+):i. a 1m
of carbon fiber (IM-6 from Herkiels 12.00
The fibers used in DE 2,658,234 had a twist of 5/-. The bottom of the tow ran through a 5 cm long glass tube. The glass tube does not create tension in the tow, and the catch basin
I rested gently on the bottom of the box to prevent the aa from getting twisted. All of the water used was deionized water, including the water used to rinse the fibers.

Treatment of the fibers was as follows: 10 minutes using Sibley's Conditioner 1160B; 5 minutes using deionized water rinsing; 1.5 minutes using 25% by volume HCI in deionized water; 3 .5 minutes using Sibley's Catalyst 9F; 5 minutes using deionized water rinse; 5 minutes using Sibley's Accelerator 19; 5 minutes using deionized water rinsing; 12 minutes using Sibley's electroless copper plating solution This solution consists of 79% deionized water by volume, 11% by volume Sibley C
P-78M, 4.5% by volume Sibley CP-78R were combined and heated to 46.1°C (115″F), then 5% by volume.
．． An 85 minute deionized water rinse prepared by adding 5% by volume of Sibley CP-78B.

When using this heated solution, a small glass evaporating dish was used in place of the polypropylene bath, and a heating plate was used underneath to maintain the temperature of the solution. The fibers were dried in a vacuum drying oven at 120°C for 15 minutes IW12.
Dry under vacuum of 5 mmHg. This device filled loosely suspended fibers with solution and unrolled the fibers. t
German patent no.
The twist induced in aJl to replicate the No. 34 example was maintained in the tow throughout the experiment. At that point, the fibers were untwisted. The final solution was pumped through untwisted fibers. This filled the fibers more completely with solution, but at a distance of approximately 20 cm from the F embankment.
One area showed some evidence of restraint. Later various analyzes surround the tow mass and join it together, [
indicated the presence of wrapper J or wandering fibers (or several fibers). The passive nature of fiber spreading by solution flow in this technique does not overcome such constraints; when the last solution was cycled, evidence of copper precipitation was seen almost immediately.

Copper precipitation was evidenced by an immediate color change as well as significant hydrogen evolution in the tow. After completing the final rinse, the fibers were dried and visually inspected. Evidence of one black zone was seen in the center of the fiber approximately 20 cm from the bottom of the tow. This area corresponded to the section believed to contain the "wrapper." The tow appeared very shiny and copper in color and was soft to the touch, but the fibers did not appear to be completely loose. This is the "overluffing" or "overluffing" of adjacent fibers. (@
It may be possible to show some evidence of the When examined by scanning electron microscopy (SEM), the fibers in the tow are non-uniform in thickness around the circumference and can have coatings that vary between 0.8 and 3.5 microns on the same fiber. Wakata. A typical diagram is shown in FIG. A coating thickness of 2.5 microns near the outside of the fibers of the tow was observed, compared to a coating as thin as 0.2 microns in the center of the tow. Tow is also
It was highly agglomerated with only 43% of the fibers being individualized in cross section. 1.2.3.4.5.
The number of aggregates containing 6 or more fibers was characterized by counting the number of aggregates containing 6 or more fibers. The percentage of all fibers contained in each size aggregate was then calculated.

The results are shown below: Number of fibers in each aggregate 1234566 % larger fibers 43199 5 4 5 15 Comparative Example 4A In Sakovieh mentioned above,
Both nickel and copper coatings from 1,500 yen
It was applied to a tow of 10,000 filament graphite fibers. The diameter of the fibers was 6.5-10 microns. Prior to electroless plating, the fibers were first treated with boiling water, a stannous chloride bath, and then a paranoum chloride bath. No residence time or concentration is stated for the solution. Equipment not listed. For the copper-plated fibers, observers stated that a glossy coating of uniform thickness was obtained on all fibers of the tow from the following electrolytes:
A: 170 g/l Seignet salt [potassium sodium tartrate 1,50 g/l sodium hydroxide, 30
g/l sodium carbonate:B:40% formaldehyde solution 1:A:B=5:1 (pH 12.3, temperature 20°C). The average settling rate was 0.03 microns/min. It should be noted that the above solutions for electrolytic deposition of copper do not contain any form of copper-containing chemicals. Therefore, we presumed that this omission was a typographical error or omission. To determine the IFi source and concentration, reference was made to the following literature known to Sakovich: F.
.

A. A. Modern Electroplating
% 3rd edition 10 Edited by Ulenheim, Ji5in 9 Illy & Sons Incorporated (
John Wiley & 5ons, Inc.
), New York, 1974. pp. 734-739. Baths very similar to those used by Sakovich are 73
This is Yu 4 listed on page 6. By comparison, multiplying the ingredients by 615, the ratios of the ingredients given were identical to those used by Sakovich.

Lourenheim Bath Sakovich CuSO4”5H2029 Omitted Tartar mKNa (g/l) 142 170NaO
H (g/l) 42 50NasCO
s (g/I) 25 30 Formaldehyde (37%) (ml/l) 191 Formaldehyde (40%) (ml/l) The solution of 1670 Urenheim also contains 17 g/l of Versene (V
ersene) T(EDTA+)reethanolamine). However, since this compound was not disclosed by Safubichi, it was not used in the electroless plating bath of this example. Since the exact composition and concentration for stannous chloride and stannous palladium chloride were not described, commercially available solutions were used for chemical precipitation of copper. These solutions are commonly used in the printed circuit board industry.

Gra7ai) Jffl fiber tow (12,000 filamen) IM-6, Hercules, no sighting, pA9
The experiment was conducted using A frame made by bending a glass rod into a rectangle has a length of 102ca + (4
0 inch) A rough loop was fixed with tape. This 7
The lame held the fibers together and kept them from floating as they were dipped into the solution. This is particularly important when placing the fibers in copper-containing solutions. This is because the formation of hydrogen gas on the fibers pushes the fibers to the surface of the bath. Four 1 liter graduated cylinders were used to hold the reaction solution. Water was heated to boiling in an Erlenmeyer flask on a hot plate and then poured into the first graduated shilling. The cylinder was heated by heating tape wrapped around it. This fiber was immersed in hot water for 5 minutes. During this period, the water temperature dropped to 92°C. Then Ii&
The fibers were transferred to a second cylinder containing a solution of stannous chloride (Sibley Accelerator 19) for 5 minutes.The fibers were then rinsed with deionized water for 2 minutes. After rinsing, #la was placed in a palladium chloride solution (Sibley Catalyst 9F) for 5 minutes. The fibers were rinsed again with ionized water for 5 minutes. After 2 minutes of rinsing, the effluent from the fibers was colorless and contained no catalyst. The fibers were then placed into a cylinder containing an electroless plating solution. This solution was prepared in the following way (as outlined by Lowenheim): 35
g of Cu5O,.5H20 was dissolved in 600 el of deionized water; 170 g of potassium sodium tartrate was added with stirring; 50 g of sodium carbonate was added to the above solution with stirring; 50 g of sodium hydroxide pellet was dissolved in 100 l of water and this solution was then slowly added to the stirred copper solution; deionized water was then added to bring the total volume of the solution to 81
and 191+el of 37% formaldehyde was added to this solution just before plating.

The solution was at room temperature and the pH was determined to be 12.2. Immediately after solution placement of the a-fiber and 7-reme, evidence of gas evolution was seen.

Foaming continued during the entire reaction time, which was 33 minutes.

This period was shown to be long enough to produce a 1 micron thick copper coating. The color of the solution is approximately 1
It changed after 5 minutes. The solution changed from clear blue to a cloudy dark blue-green. At the end of the reaction time, rinse the fibers and incubate in a vacuum oven at 120 °C for 15 min at 25 simH.
Dried under vacuum at 100 g.

The fibers were visually inspected and cross-sections were prepared for SEM analysis. Three 3.8 cm (1.5 inches) were cut from the tow of fibers for consolidation into a composite.

Visual inspection of the fibers showed excessive copper agglomerates on the tow.

The color of the metal plating was a dark reddish brown. The inside of the toe was not easy to see.

Because the outside of the bundle was covered in dark powdered steel.

When the tow-bearing cross-section was examined by scanning electron microscopy, the following was observed: The thickness of the coating was relatively uniform around the circumference of the fiber, but the thickness varied from fiber to fiber. did. A typical diagram is shown in FIG. The minimum thickness seen was 0.32 microns and the maximum was 1.54 microns. The average thickness is 0.
98 microns with a standard deviation of 0.43 microns. Only 43% of the fibers were individualized.

The agglomeration was characterized as Comparative Example 3A; the results are listed below: Number of fines in each agglomerate 1234566 % larger fibers 431613 7 4 4 12 Comparative Example 4
A Kuzmin (Kuz' win) (USSR)
Patent No. 489,585 discloses that in order to improve the physical and mechanical properties of copper-graphite composites, a coating of a-fiber copper is first carried out by chemical precipitation, and then it is subjected to a conductive coating. Precipitate at 920~ while hot press
It teaches carrying out at 980'C under pressure of 35-250 kg/cm2. In a paper published by the same experimenter, the fibers of all elements are coated with a uniform layer of metal in the method of chemical precipitation. Although this experiment is not fully described in either the patent or the paper, it is possible to synthesize the procedure between the two documents. The experiments in this document were carried out on carbon fibers produced in the form of twisted tows of 7.2000 element fibers of 5.9 micron diameter with a bean-shaped cross section. The fibers were oxidized by holding them in 65% nitric acid for 5 minutes.

In the next step, an acidified palladium chloride bath was used to activate the surface. This patent specifies a pH of 3-4, but does not list concentrations. Treatment in stannous chloride solution was then carried out for 10 minutes. No specific concentration or pH is listed. Careful washing of the fibers with running water during processing is recommended.

Great paper! The electroless copper plating solution described in both patents is an alkaline solution containing copper sulfate, formaldehyde, potassium sodium tartrate, and sodium diethyldithiocarbonate. Although the two commercial sources do not have the chemical designation sodium diethyldithiocarbonate, sodium noethyldithiorubamate is listed and is known to be used as a chelating agent. Thus, the use of carbonate was interpreted as a typographical error. Neither the patent nor the journal article describes the concentrations of common ingredients in the plating. However, a comparison with the above-mentioned Lorenheim reference suggests possible bath configurations. The coating thickness is stated to be 0.1 to 0.4 microns for a residence time of 3 to 6 minutes. 1 onto graphite fiber! The clothing is described in more detail. The solution to be used is 260 g/l C
u Prepared by combining SOI 5H20 and 60 of/l sulfuric acid and 2-5 amperes 71
Plating is carried out for 4 hours at a current density of 00 cm" and pH 1-2. They report that the consolidation into composites is carried out in vacuum for 30 minutes at a temperature of 940 °C and under pressure of 50 kg/fiber". do. This method will produce a composite with a fiber fraction of 5% by weight.
In this paper, it is explained that scanning microscopy of some of the composites showed defects in the composites, including "clumps of fibers, pores in the matrix."

Four 1 liter graduated cylinders were filled with the recommended solution. Seven frames made by bending six rods into a rectangle were used to hold the fibers. (!The fiber used has a length of 1
02es+ (40 inches) of 12.000 filament IM-6 graphite fiber (Herkiels, 7 micron fiber), which was attached to 7 rams, 10 twists were introduced into the fiber, and the second end was It was fixed with tape to the top of the 7-frame. The fibers and 7 lemons were soaked in 65% nitric acid for 5 minutes, then thoroughly rinsed with deionized water. for a minute and carefully rinsed with deionized water.

The fibers and seven reams were treated for 10 minutes in a bath of a solution of stannous chloride (Sibley Accelerator 19). Following the stannous chloride bath, the fibers were thoroughly rinsed.

The solution for electroless deposition was prepared in the following way: 13. Cu5O,-5H,O was dissolved in 80011+7) deionized water; 66 g potassium sodium tartrate was added with stirring; 50 g carbonate Sodium was added to this solution with stirring; 0.018 g of sodium diethyldithiocarbamate was added to the above solution with stirring; 19.3 g of sodium hydroxide was dissolved in 100 l of deionized water and then this solution was added slowly to the stirred copper solution; deionized water was then added to bring the total volume of the solution to 96
and 381 37% formaldehyde was added to this solution just before plating.

The solution was at room temperature for fiber treatment.

The fibers and frame were immersed in the plating solution for a total of 5 minutes. The Ia fibers were carefully cleaned at the end of the 6wc electroplating period when the surface of the fibers showed evidence of soot formation upon immersion in the solution. An electroplating light solution was prepared by dissolving 1040 g of CuSO4.5H20 in 3.5 liters of deionized water with stirring. The solution was heated slightly to dissolve all the copper sulfate in this volume of water. The solution was then cooled to room temperature. After cooling, 2401 sulfuric acid was carefully added to the solution.

Deionized water was then added to bring the total volume of the solution to 4 liters. Electroplating is carried out in a tank (Fig. 8),
This layer contained an anode of 0FHC grade copper rod stock. The cathodes were two sections of copper tubing, both of which supplied electrical current. Each end of the fiber was wrapped around the cathode roller. 2 sections of fiber approximately 125 cm long
The book was held below the surface in solution by a bent glass rod.

The power supply was started and the current was controlled. The current is 5
The amperage increased slowly. The cathode and the fiber compartment between the cathode and the solution surface were kept cool by spraying this compartment with water from a plastic rinse bottle. After approximately 20 minutes, the fibers began to spark near the intersection of the fiber and solution interface. At this point, the experiment was stopped.

The fibers are removed from the bath, rinsed and then placed in a vacuum oven for 15 minutes.
Dry in a vacuum of 25 mmHH for minutes.

Small sections of fiber were cut and prepared for scanning electron microscopy. Visual inspection of the tow showed areas with incomplete coverage. The fibers did not spread easily, suggesting that adjacent fibers were plated together. Three small sections of fiber were removed and used to prepare composite samples. Visual inspection also showed that the fiber coverage was incomplete. This was confirmed by SEM analysis. Although the cross section of the fiber tow showed relatively good uniformity of coating thickness around the circumference, the variation in coating thickness from fiber to fiber in the tow was very large. Many of the fibers in the center of the tow are uncoated;
A thick coating of about 20 microns was found near the surface of the tow. A typical drawing is shown in FIG.

The agglomeration was severe, with only 7% of the fibers being individualized. The aggregation was as follows: Number of fibers in each agglomerate 1234566 % larger fibers 7 5 4 4 4 3 35 Additionally, 36% of the fibers were uncoated.

Comparative Example 6A Japanese Patent No. 70-Nia 095 (1985
) teach that electroplating of graphite fibers in a copper electroplating bath without brighteners creates a matte coating that is less stable during knitting into fabrics due to the roughness of the coating. There is. As this patent states,
The objective is to produce copper-coated carbon fibers with improved resistance to discoloration and solderability. A number of electroplating coatings are discussed and the availability of suitable brighteners is guaranteed. For example, UBAC-1 (trade name OMI Carp) is used in a copper sulfate bath;
And copper ryumu (product name MKTCo)
) are used in cyanide baths. In practical example 1, a carbon fiber bundle consisting of 3,000 single fibers with an average diameter of about 7 (microns) was prepared and pretreated at about 500°C and coated with a copper-plated alloy containing a brightener. Composition: Copper sulfate 100g/I, sulfur fi 100g/l, brightener UBAC-110 1/LCI ″″ 10pp
m) at an average current density of 6 A/d+s2, producing a copper plated layer 2 (microns) thick. This was compared with a sample containing no brightener in terms of gloss and solderability.

For comparison purposes, 12 sections of IM-6 graphite fibers of 1.5-length were drawn into a tube furnace heated to 500°C. The fibers were kept at this temperature and treated in air for 5 minutes. Mark the center of this tow length, 76.2e (30 inches), and add a total volume of 8 liters of Solution I used for electroplating according to the description of this patent. It was prepared in a liter Erlenmeyer-7 Rasp. The procedure for ** was as follows: Stir together the following ingredients: 3 liters deionized water; 400 g CuSO4.5 H20; 400 ml sulfuric acid; 401 UBAC-1 brightener; Up -0,33
ml of 35% HCI acid solution.

Electroplating was carried out in a bath (Figure 8) containing an anode of 0FHC grade copper rod stock. The cathodes were two sections of steel tubing, both of which were supplied with electrical current. Each end of the fiber was wrapped around the cathode roller. length almost 5
A section of 0.8e (20 inches) #l fiber was held below the solution using two bent glass rods.

The power supply was started and the current was controlled. The current was slowly increased to 5 amps. The cathode and the fiber compartment between the cathode and the solution surface were kept cool by spraying this compartment with water from a plastic rinse bottle. After approximately 20 minutes, the fibers began to spark near the intersection of the fiber and solution interface. At this point, the experiment was stopped. The fibers are removed from the bath, rinsed and then placed in a vacuum oven for 1
Dry in a vacuum of 25 mmHH for 5 minutes. Small sections of fiber were cut from the tow and evaluated by scanning electron microscopy. Visual inspection of this tow showed some areas of incomplete coverage; 0 quality was unsuitable for hot pressing. A typical diagram is shown in FIG. The fibers did not spread easily, suggesting some evidence of plating of adjacent fibers together.

SEM analysis of the cross section of two tows showed the following facts: Uniformity around the circumference: very poor, eg 14.7-3.5 microns on a single fiber.

Minimum thickness: 20 microns (uncoated) Maximum thickness: 38 microns Agglomeration: Number of fibers in each aggregate 1234566% of larger a fibers 51106 3 1 2 12 Additionally, 15% of the fibers are uncoated , or only partially coated.

Comparative Examples 7A to 9A Using the fibers prepared in Comparative Examples 3A to 5A, 1
It was formed according to the hot press technique described in the above-mentioned document published in 1975. (2 sheets of flexible graphite) (POCOG graphite).

Lay down the fiber section with a D ecaturel T
The treatment was carried out by combining in an atmosphere of 3% hydrogen and 97% nitrogen under a pressure of . The heating time for the hot press (Figure 9) was 1 hour and 35 minutes.

Once the furnace was cooled to 250°C, the samples were removed. They were then encapsulated in epoxy for morphological examination, sectioned, and polished for microscopic analysis.

Each of the composites had voids, delamination, matrix-rich placement, and, in the case of the fibers of Comparative Example 5A, large unconsolidated zones due to the uncoated fibers in the coated tow. . Comparative Examples 7A-9
The photographs of the complex in A are shown in tItJ14 to Figure 1, respectively.
It is shown in Figure 6.

As the above comparative data demonstrate, when the teachings of the prior art are followed, a relatively thick, uniform, hard and adherent layer of copper is not deposited on a carbon core, despite claims to the contrary. Moreover, the results show that homogeneous, substantially void-free composites are not obtained by hot pressing fibers prepared according to the prior art.

The patents, publications, patent applications, publications of technical information and test methods mentioned above are hereby incorporated by reference.

Many modifications of the invention will be apparent to those skilled in the art in light of the above detailed description. For example, instead of carbon fibers, alumina fibers can be used. All such obvious modifications are fully within the intended scope of the invention as defined in the claims.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of the plating method according to the present invention. Figure tJIJ2 is a perspective view of a dammed plating tank preferred for use in the present invention. Figure 3a is a plan view of a beater rod arrangement preferred for use in the present invention. Figure 3b is a side view of the beater rod arrangement of Figure 3a. FIG. 4 is a schematic diagram of a heat press apparatus suitable for use in the present invention. FIG. 5a is a semi-schematic illustration of manufacturing an elongated forming pellet of the present invention. FIG. 5b is a semi-schematic illustration of a method of mixing and forming the elongate slivers of the present invention into shaped articles. FIG. 6 is a photomicrograph of a cross-section of a copper-coated fiber of the present invention in resin matrix 177, cut perpendicular to the length of the fiber. Figure 7 shows Schmidt's German patent No. 2,658.2.
34 is a schematic diagram of a fiber plating apparatus used in electroless deposition of metals according to No. 34. FIG. 8 is a cross-sectional view of an electroplating bath commonly used in this field. FIG. 9 is a schematic diagram of a heat press apparatus suitable for use in the present invention. Figure 10 shows Schmidt's German Patent No. 2,65 in a resin matrix cut perpendicular to the fiber length.
8,234 is a micrograph of a cross section of the copper-coated fiber. FIG. 11 is a micrograph of a cross-section of the copper-coated fiber of Sakovich et al. FIG. 12 is a photomicrograph of a cross-section of a copper-coated fiber of Kuzmin Soviet (USSR) Patent No. 489.585 in a resin matrix cut perpendicular to the length of the fiber. Figure 13 shows Yoshi Sairiki et al.'s Japanese Patent Application No. 70-170 in a resin matrix cut perpendicular to the length of the fibers.
It is a micrograph of the cross section of the copper coated fiber of No. 95. Figure 14 shows Schmidt's German Patent No. 2,65 in a resin matrix cut perpendicular to the length of the fibers.
FIG. 8,234 is a micrograph of a cross-section of the united copper-coated fibers. FIG. 15 is a photomicrograph of a cross-section of the consolidated copper-coated aJI of Sakovich et al. FIG. 16 shows the united copper coating #lJ1 of Kuzmin Soviet (USSR) Patent No. 489,585 in a resin matrix, cut perpendicular to the fiber length! This is a micrograph of a cross section of. FIG. 17 is a photomicrograph of a cross-section of a clustered copper-coated fiber of the present invention in a -axial configuration cut perpendicular to the length of the fiber. FIG. 18 is a photomicrograph of a cross-section of a consolidated copper-coated miscellaneous material of the present invention in a cross-overlapping configuration. 2 Storage roller 4 Bath 6 Die 8 Furnace 10 Treated filament 12 Shredder 14 Container 16 #l fiber pellet 18 Resin pellet 20 Compounded mixture 22 Hopper 24 Forming press 26 Cylinder 28 Mold 30 Molded article FIG. 4 RI-RI MAU A-11 FIG, 7 FIG, 9 Procedural amendment (1 button December 11, 1988 Director General of the Patent Office Kunio Ogawa 1, Indication of case Patent Application No. 277255 of 1988 2, Name of the invention: Copper-coated fiber 3. Relationship with the person making the amendment: Name of the patent applicant: American Cyanamid Company 4, Agent: 107 5. Date of amendment order: None. 6. Subject of the amendment: ' Patent claims in the description The content of the amendment in Column 7, “Scope of providing a plurality of metalloid core fibers; (b) immersing at least a portion of said length of fiber in a bath comprising a wetting agent in an aqueous medium; and (c) electroless deposition of a metal comprising copper. (d) immersing at least a portion of said length of fiber in a bath capable of sensitizing said fiber to a bath capable of electrolessly plating said fiber with a metal consisting of (6) immersing at least a portion of the fiber in a bath that results in electrolytically depositing a metal comprising copper; f) applying an external voltage between the fiber and the bath sufficient to deposit a metal consisting of copper onto the fiber, and applying the voltage and resulting current to the core for at least one
The process (1) is maintained for a sufficient period of time to produce a relatively thick, uniform, hard-bonded, conductive layer of copper, and while applying low tension to the yarn or tow and spreading the fibers ( A method for producing a continuous thread or tow of composite fibers, characterized in that it comprises carrying out steps b) to (f). 3. The method of claim 1, wherein the thickness of the one or more layers of metal on the thread or tow ranges from about 0.6 to about 3.0 microns. 5. The method of claim 4, wherein the thickness is at least about 0.8 microns. 5. The method of claim 4, wherein the thickness is at least about 1.2 microns. 6. 7. The method of claim 1, wherein the standard deviation of the coating thickness is less than 30% of the average coating thickness both around the circumference of each fiber and from fiber to fiber. The method of claim 1, wherein the majority of the fibers are individualized and non-agglomerated. 8. The method of claim 1, wherein more than about 70% of the fibers are individualized and non-agglomerated. The method of claim 7. 9. The method of claim 8, wherein more than about 80% of the fibers are individualized and non-agglomerated. 10. The core is carbon, graphite, polymer, 11. The method of claim 1, wherein the core is made of glass, ceramic, or any combination thereof. 11. The method of claim 1, wherein the core is made of carbon. 12. A semimetallic core; An article consisting of a continuous yarn or tow of composite fibers present on said core, characterized in that it has one relatively thick, uniform, tightly bonded, electrically conductive layer of copper. 13. @Acid component: (,) A continuous yarn or tow consisting of composite fibers, said yarn or tow consisting of a semi-metallic core and at least one relatively thick, uniformly tightly bonded copper on said core. and (b) a matrix consisting of (i) a metal or (ii) an organic polymeric material, wherein the fibers are arranged in the matrix. 14. An injection molding compound consisting of elongated granules, each of the granules containing a bundle of elongated composite fibers, the composite fibers having a semimetallic core and on the core, the composite fibers having at least one layer. a relatively thick, uniform and tightly bonded conductive layer made of copper, the fibers extending substantially parallel to each other in the longitudinal direction of the grains, and a thermally stable film forming property. The injection molding compound is characterized in that one or more layers of the metal are dispersed substantially uniformly throughout the granules in a thermoplastic adhesive. 15. A continuous yarn or tow according to any of claims 12-14, having a thickness of about 0.6 to about 3.0 microns. 16. The continuous yarn or tow of claim 15, wherein said thickness is at least about 0.8 microns. 17. The continuous thread or tow of claim 16, wherein said thickness is at least about 1.2 microns. 18. The standard deviation of the coating thickness is both around the circumference of each fiber and from aJll to the fiber:
A continuous yarn or tow according to any of claims 12 to 14, which is less than 30% of the average coating thickness. 19. A continuous yarn or tow according to any one of claims 12 to 14, wherein the fibers are mostly individualized and non-agglomerated. 20. A continuous yarn or tow according to any of claims W112-14, wherein more than about 70% of the fibers are individualized and non-agglomerated. 21. 21. The continuous yarn or tow of claim 20, wherein more than about 80% of the fibers are individualized and non-agglomerated. 22. The continuous yarn or tow according to any one of claims 12 to 14, wherein the core is made of carbon, graphite, polymer, glass, ceramic, or any combination thereof. 23. The continuous thread or tow according to any one of claims 12 to 14, wherein the core is made of carbon.'' Written amendment (released) February 19, 1988 Commissioner of the Japan Patent Office Small Mr. Kunio Kawa■, Indication of the case Patent Application No. 277255 of 1988 2, Name of the invention Copper-coated fiber 3, Relationship to the case by the person making the amendment Name of the patent applicant Name American Cyanamid Company 4, Agent Address: 107 5. Date of amendment order January 26, 1988 (shipment date) 6゜The column for the brief description of the drawings in the specification subject to amendment is corrected as follows. (1) On page 125 of the specification, lines 9 to 12, “3rd
Figure a is a... side view. ” and “3rd
The figures are top and side views of a preferred beater rod arrangement for use in the present invention. ” he corrected.

Claims (1)

[Claims] 1. A composite material, characterized in that it has a semimetallic core and at least one relatively thick, uniform, tightly bonded electrically conductive layer of copper present on said core. A continuous thread or tow of fibers. 2. The thickness of the one or more layers of metal is about 0.6~
A continuous thread or tow as claimed in claim 1 in the range of about 3.0 microns. 3. The continuous yarn or tow of claim 2, wherein said thickness is at least about 0.8 microns. 4. The continuous yarn or tow of claim 3, wherein said thickness is at least about 1.2 microns. 5. The continuous yarn of claim 1, wherein the standard deviation of the coating thickness is less than 30% of the average coating thickness both around the circumference of each fiber and from fiber to fiber. Or tow. 6. A continuous yarn or tow according to claim 1, in which the majority of the fibers are individualized and non-agglomerated. 7. The continuous yarn or tow of claim 1, wherein more than about 70% of the fibers are individualized and non-agglomerated. 8. The continuous yarn or tow of claim 7, wherein more than about 80% of the fibers are individualized and non-agglomerated. 9. The continuous yarn or tow of claim 1, wherein the core is comprised of carbon, graphite, polymer, glass, ceramic, or any combination thereof. 10. The continuous yarn or tow according to claim 1, wherein said core is made of carbon. 11. A cloth fabric characterized by being woven, braided, or knitted from the threads described in claim 1 alone or from a combination of threads of different materials and the threads. 12. A nonwoven sheet, characterized in that it is deposited from the yarns described in claim 1 alone or from a combination of yarns of different materials and the yarns. 13. A three-dimensional fabric characterized by being manufactured by weaving, braiding, knitting or depositing the yarn described in claim 1 alone or a combination of yarns of different materials and the yarn. Manufactured articles. 14. A composition comprising a cut product of the thread or tow according to claim 1. 15. A composition according to claim 14, adapted for use in reflecting radar, wherein the thread or tow is cut to a length related to the wavelength of one or more radar frequencies. 16. The layer of copper is deposited on the core by a two-step process, the first step comprising electroless deposition and the second step comprising electrolytic deposition. A continuous thread or tow. 17. A single fiber recovered from the continuous yarn or tow according to claim 1. 18. Steps: (a) providing a plurality of continuous lengths of metalloid core fibers; (b) immersing at least a portion of said lengths of fibers in a bath consisting of a wetting agent in an aqueous medium; c) immersing at least a portion of said length of fiber in a bath capable of rendering the fiber susceptible to electroless deposition of a metal comprising copper; and (d) electrolessly immersing said fiber with a metal comprising copper. immersing at least a portion of the length of fiber in a bath capable of plating;
depositing an electrically conductive layer of the metal on the fiber; (e) immersing at least a portion of the fiber in a bath capable of electrolytically depositing a metal comprising copper; and (f) immersing the fiber in the bath. while applying an external voltage sufficient to deposit a metal consisting of copper onto the fiber, and applying the voltage and resulting current to the core at least once.
step (b) while applying low tension to the yarn or tow and spreading the fibers; ) to (f). 19. The method according to claim 18, which is carried out continuously. 20. The method of claim 18, wherein the thickness of the one or more layers of metal on the thread or tow ranges from about 0.6 to about 3.0 microns. 21. The method of claim 19, wherein said thickness is at least about 0.8 microns. 22. The method of claim 21, wherein the thickness is at least about 1.2 microns. 23. The method of claim 18, wherein the standard deviation of the coating thickness is less than 30% of the average coating thickness both around the circumference of each fiber and from fiber to fiber. 24. The method of claim 18, wherein the majority of the fibers are individualized and non-agglomerated. 25. The method of claim 24, wherein more than about 70% of the fibers are individualized and non-agglomerated. 26. The method of claim 25, wherein greater than about 80% of the fibers are individualized and non-agglomerated. 27. The method of claim 18, wherein the core comprises carbon, graphite, polymer, glass, ceramic, or any combination thereof. 28. The method of claim 18, wherein said core comprises carbon. 29. The method according to claim 18, comprising the step of weaving, braiding or knitting the yarn produced by the method alone or a combination of yarns of different materials and the yarn to make cloth. 30. The method of claim 18, comprising the step of depositing the yarn produced by the method alone or in combination with yarns of different materials into a nonwoven sheet. 31. The method of claim 18, comprising weaving, braiding or knitting the material into a three-dimensional manufactured article. 32. The method of claim 18, including the step of cutting the yarn produced by the method into shorter lengths. 33. The method of claim 18, comprising cutting the produced yarn or tow into lengths related to the wavelength of one or more radar frequencies. 34. The method of claim 18, wherein the sensitizing bath (c) comprises a colloidal suspension of palladium and tin chlorides. 35. The method according to claim 18, wherein the electroplating bath (e) comprises a copper pyrophosphate plating bath. 36. The method of claim 31, wherein the bath also includes a stabilizing amount of mercaptobenzothiazole, alone or in combination with 2,2-bipyridyl. 37. A composite fiber yarn or tow produced by the method according to claim 18. 38. A single fiber, characterized in that it is recovered from a continuous yarn or tow produced by the method according to claim 18. 39. Components: (a) a continuous thread or tow of composite fibers, said thread or tow comprising a semimetallic core and at least one relatively thick, uniformly and tightly bonded electrically conductive layer of copper on said core; and (b) a matrix of (i) a metal or (ii) an organic polymeric material, the fibers being disposed within the matrix. 40, the thickness of the one or more layers of metal is about 0.6
Claim 39 in the range of ~3.0 microns
Compositions as described in Section. 41. The composition of claim 40, wherein said thickness is at least about 0.8 microns. 42. The composition of claim 41, wherein said thickness is at least about 1.2 microns. 43. The composition of claim 39, wherein the standard deviation of the coating thickness is less than 30% of the average coating thickness both around the circumference of each fiber and from fiber to fiber. 44. The composition of claim 39, wherein the majority of the fibers are individualized and non-agglomerated. 45. The composition of claim 44, wherein more than about 70% of the fibers are individualized and non-agglomerated. 46. The composition of claim 45, wherein greater than about 80% of the fibers are individualized and non-agglomerated. 47. The composition of claim 39, wherein the core comprises carbon, graphite, polymer, glass, ceramic, or any combination thereof. 48. The composition of claim 39, wherein the core comprises carbon. 49. The composition of claim 39, wherein the thread or tow (a) is cut. 50. The layer of copper is deposited on the core by a two-step process, the first step comprising electroless deposition and the second step comprising electrolytic deposition. Composition of. 51. The composition of claim 39, wherein the composite fibers (a) are woven or knitted into the reinforcing structure in parallel, substantially parallel relationship. 52. The metal matrix (b) is copper, aluminum, lead, zinc, silver, gold, magnesium, tin, titanium,
40. The composition of claim 39 comprising iron, nickel, alloys, or any combination thereof. 53. The composition of claim 52, wherein said metallic matrix comprises copper. 54. The core is made of graphite, the metal layer is made of copper, the copper layer is about 0.6-3.0 microns, the metal matrix is made of copper, and the graphite fibers are arranged in parallel. 40. The composition of claim 39, wherein the composition is arranged in substantially parallel relationship. 55, the steps of: (a) providing a continuous metal-coated thread or tow according to claim 39; and (b) structuring a matrix of metal around the metal-coated fibers. 1. A method of manufacturing an article comprising: forming a composite material. 56. The method of claim 55, wherein the metal matrix is constructed around a coated filament by powder technology techniques, casting or pultrusion. 57. Components: (a) fibers of a metalloid core, and (b) a metal matrix consisting of copper, the core fibers being uniformly distributed throughout the thickness of the metal matrix. CLAIMS 1. An article of manufacture comprising a region substantially free of voids and substantially matrix-free. 58, produced by direct consolidation under heat and pressure of a continuous thread or tow of composite fibers, said thread or tow having a majority core and on said core at least one relatively thick, uniform, stiff 58. The article of claim 57, having an electrically conductive layer of copper adhered thereto. 59, the thickness of the one or more layers of metal is about 0.6
Claim 58 in the range of ~3.0 microns
Items listed in section. 60. The article of claim 59, wherein the thickness is at least about 0.8 microns. 61. The article of claim 60, wherein the thickness is at least about 1.2 microns. 62. The article of claim 58, wherein the standard deviation of the coating thickness is less than 30% of the average coating thickness both around the circumference of each fiber and from fiber to fiber. 63. The article of claim 58, wherein the majority of the fibers are individualized and non-agglomerated. 64. The article of claim 63, wherein more than about 70% of the fibers are individualized and non-agglomerated. 65. The article of claim 64, wherein greater than about 80% of the fibers are individualized and non-agglomerated. 66. The composition of claim 39, wherein said matrix (b) is an organic polymeric material. 67. The composition of claim 66, wherein the organic polymeric material is substantially non-conductive. 68. The organic polymer material is polyester, polyether, polycarbonate, epoxide, epoxy-novolac, epoxy-polyurethane, urea-type resin, phenol-formaldehyde resin, thiourea resin, melamine resin, urea-aldehyde resin, alkyd resin, polysulfide. resin, vinyl organic prepolymer resin, polyfunctional vinyl ether, cyclic ether, cyclic ester, polycarbonate co-ester, polycarbonate co-ester
67. The composition of claim 66 selected from the group consisting of silicone, polyetherester, polyimide, polyamide, polyesterimide, polyamideimide, polyetherimide, and polyvinyl chloride. 69, the organic polymer material (i) comprises the composite fiber (
Claim 6, present together with a woven, braided, knitted or non-woven fabric foil, sheet or mat consisting of a)
An article of manufacture characterized in that it comprises a composition according to item 6. 70, the organic polymer material (b) comprises the composite fiber (
Claim 6 reinforced with a woven, braided, knitted or non-woven fabric foil, sheet or mat consisting of a)
A manufactured shaped article characterized in that it is formed from the composition according to item 6. 71. Claim 39, wherein said organic polymeric material (b) is reinforced with composite fibers (a) in comminuted form.
Compositions as described in Section. 72. The organic polymer material (b) is an epoxy;
67. The composition of claim 66, wherein the conductive core of the composite fiber (a) is carbon and the conductive metal layer is formed from copper. 73. An injection molding compound consisting of elongated granules, each of the granules containing a bundle of elongated composite fibers, the composite fibers having a semimetallic core and on the core, the composite fibers having at least one layer. a relatively thick, uniform and tightly bonded conductive layer made of copper, the fibers extending substantially parallel to each other in the longitudinal direction of the grains, and a thermally stable film forming property. The injection molding compound is substantially uniformly dispersed throughout the granules in a thermoplastic adhesive. 74, the thickness of the one or more layers of metal is about 0.6
Claim 73 in the range of ~3.0 microns.
Injection molding compound as described in Section. 75. The injection molding compound of claim 74, wherein said thickness is at least about 0.8 microns. 76. The injection molding compound of claim 75, wherein said thickness is at least about 1.2 microns. 77. The injection molding compound of claim 73, wherein the standard deviation of the coating thickness is less than 30% of the average coating thickness both around the circumference of each fiber and from fiber to fiber. . 78. The injection molding compound of claim 73, wherein the majority of the fibers are individualized and non-agglomerated. 79. The injection molding compound of claim 78, wherein more than about 70% of the fibers are individualized and non-agglomerated. 80. The injection molding compound of claim 79, wherein greater than about 80% of the fibers are individualized and non-agglomerated. 81. The injection molding compound of claim 73, wherein said core comprises carbon, graphite, polymer, glass, ceramic, or any combination thereof. 82. The injection molding compound of claim 73, wherein said core comprises carbon. 83. The adhesive comprises a combination of: (a) poly(C_2-C_6 alkyloxazoline) and (b) poly(vinylpyrrolidone), wherein the adhesive substantially surrounds each said filament. An injection molding compound according to Range 73. 84. The injection molding compound of claim 73, wherein component (b) comprises from about 7.5 to about 75% by weight of the combined weight of components (a) and (b). 85, the granules are about 0.05 to about 0.48 cm (about 1/
74. The injection molding compound of claim 73, having a diameter of 48 to about 3/16 inch. 86, the granules are about 0.08 to about 0.32 cm (about 1/
74. The injection molding compound of claim 73, having a diameter of 32 to about 1/8 inch. 87. The injection molding compound of claim 73, wherein the amount of thermoplastic adhesive is not substantially greater than an amount that maintains the integrity of the fiber bundle during handling. 88, reinforcing filament is 67.5-97.5% by volume
74. The injection molding compound of claim 73, wherein the thermostable film-forming adhesive comprises from 2.5 to 32.5% by volume. 89, the reinforcing filaments constitute 85-95% by volume and the heat-stable film-forming adhesive corresponds to 5-95% by volume.
88. The injection molding compound of claim 87 comprising 15% by volume. 90. The injection molding compound of claim 74, wherein the thermoplastic adhesive comprises poly(ethyloxazoline). 91, poly(ethyloxazoline) is about 50,000~
91. The injection molding compound of claim 90 having a molecular weight in the range of 500,000. 92. The injection molding compound of claim 74, wherein the thermoplastic adhesive comprises poly(ethyloxazoline) and poly(vinylpyrrolidone). 93, poly(vinylpyrrolidone) is about 10,000-2
93. The injection molding compound of claim 92 having a molecular weight in the range of 20,000. 94, an injection molding composition comprising: (i) molding particles of thermoplastic resin; and (ii) the elongated particles according to claim 1; The amount of (ii) is (i
)+(ii). 95. In an injection molding process, an injection molding process comprising a mixture of (i) thermoplastic molding granules; and (ii) an effective amount of the elongated granules of claim 1 to provide reinforcement. An injection molding method characterized by the step of forcing the composition into a mold.