JPS60211073A - Substrate coated by plasma increasing chemical vapor deposition, and apparatus and method for producing the same - 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 te), e.g. carpon mIIi, filaments, fibrils, films, ribbons, sheets, plates, etc., can be deposited by plasma enhanced chemical vapor deposition (plasma enhanced chemical vapor deposition) using a capacitively coupled plasma. enhanced chemistry
Relating to the use of a substrate as one of the radio frequency electrodes in a cal vapor deposition process. Substrates treated in this way, or post-treated, for example by vapor phase grafting, exhibit significantly altered or modified surface properties. The present invention also provides for the use of ceramic or organic polybu materials made in combination with dissimilar ones, which have been subjected to the above-described treatment.
The present invention relates to composites in which the article exhibits various improved physical properties such as increased mechanical strength.

Composite materials made of ceramics or plastics reinforced with materials of various origins such as glass, carbon, synthetic fibers, silicon carbide, boron, etc.
In automobiles, office equipment, sporting goods, and also in many other areas, materials made of heavier or less strong materials such as aluminum, steel, titanium, vinyl polymers, nylons, polyesters, etc. It has come to be used in a wide range of ways to replace parts. The composite material consists of two or more components, at least one of which defines the continuous phase or "matrix" and at least one other which defines the reinforcement for assembly.

One common problem when using reinforcements in such composites is the ability to transfer their properties to the materials with which ultimate and intimate contact is to be made, such as ceramics or thermoset polymers. This is something that is visually lacking. This leads to a loss of properties due to the lack of adhesion between the matrix components making up the composite and the reinforcing means. The prior art is replete with attempts to improve the adhesion between the matrix and the substrate by applying various surface treatments to the reinforcement, including various chemical, electrochemical and physical, mechanical processing, etc.

For example, the carbon substrate consists of being photo-oxidized,
Although surface treatment is often performed after installation,
This improves the shear strength between the layers in the composite material. Additionally, many such substrates are also provided with a sizing in the form of a polymer that is compatible with the epoxy or polyimide matrix resin. Although such techniques are relatively simple and low cost, they have a limited range of applications. Other techniques have also been proposed, such as acid treatment, ammonia treatment, carbide coating, carbon dioxide treatment, electrolysis treatment, irradiation, isocyanate treatment, metal halide treatment, organometallic treatment, whisker crystallization, etc. Ion plating processes, including plasma-assisted ones, are described in numerous patents and publications. For example, S. C. Sunday, Proceedings
Fifth Metal Matrix Compos
ites Technology Conference
, May 1983, P. Nos. 27-1 to 27-11 deal with ion-blating onto fibers, in which the brating layer is ultimately converted into a continuous matrix phase of the composite material. U.S. Pat. Nos. 3,904,505 and 3,961,10 to Ai Senberg.
No. 3 uses an externally generated plasma to accelerate ion blating, in this example the substrate is radio frequency excited. Induced plasma assisted deposition is described in three papers by K.R.Linger: COMPsites (G,B,)V
ol, 8. No.

31pp, 139-44. July 1977: VOrab
drucke Plansee Sem1n, 9th,
1977.2. D12/1-DI2/4 and Proc
-Conf, Ion-Plating A11ied
Tech, 1977° 223-9°; and other such treatments, Toh.

Be5lOn Co., as disclosed in the following patents:
Special Publication No. 58,120,876 (1983) (C, A
, 100:8406r), ion bombardment and ion brating;
9) (C, A, 92:202O2375, ion brating; Tokko Shokan No. 79, 162, 690 (1979
) (C8A, 92: 202376n), also ion brating;
978) (C, A, 90 Near 5547a), Plasma Etching and Ion Blating: Tokko Shokan 78.
No. 66.831 (1976) (C0A, 90:1103
2w), plasma m+7 ching and ion brating;
, A, 89:91997s), ion brating;
Tokuko Showan No. 78.38, 791 (1978) (C, A,
89:202717n), ion blating, laminating and hot pressing; and Tokuko Showan 77.2
No. 7,826 (1977) (C, A, 87:43143
n), plasma etching and ion blating, plasma spray coating techniques are also known, e.g. C, A, 96:56379e, where:
The metal comes out as fine particles that are deposited on the fibers.

Other plasma treatments are also known, such as Ro.

No. 3,723,289, U.S. Pat. No. 3,824.
No. 398 and No. 3.780.255 and Hou (
7) U.S. Patent Nos. 3,762,941 and 3.767
．． No. 774, surface modification by treatment with plasma-generated heat with carbon-H and M
There is a cathode sputtering modification of the outer surface in US Pat. No. 3,813,282 to Asotti et al. Houc7) U.S. Pat. No. 3,74
No. 5,104 and No. 3,853,600, it is deposited from a plasma as a coating on carbon. The 1983 Japanese Patent Publication No. 70.770 of FujimOri et al. vaguely describes the use of plasma-assisted chemical vapor deposition of silicon carbide onto 20IL carbon m-fibers to increase tensile strength, but no beneficial effects were found. Also of interest in this connection is plasma-assisted ion blating using sputtering, as reported by Sumitomo Electric Ind, 1
7) Special public Shokan No. 8070-769 (1983) (C, A
, 99=14622W), Special Publication No. 8060063 (
1983) (C, A, 99: 144596), and Mitsubishi Electric Corp.
Tokuko Showan No. 81, 140.021 (1981) (C,
A, 96:71290n) by deposition of silane and methane in an induced plasma. Sung, Dagl i and Yin ng.
surface modification by plasma treatment of graphite substrates, both blocks and fibers, in the 37th Annual
Conference, Re1nforced Pla
stics/ComposItes In5titut
e, The 5ociety of the Plus
tics Industry, Inc., 1982 1
March 11th to 15th, 5ession 23-B, pages 1 to B. Although the technique used was to use an inductively coupled plasma, it is also disclosed that gas phase grafting can also be achieved in which the substrate is not excited.

Composites made from fibers modified with this technique have a lower transverse rupture strength than those made from untreated fibers, but are better (though "not appreciably")
It had interlaminar shear strength. What is also interesting is Toray Industries, Inc., Special Publication No. 72, 24.979 (1972) (C, A, 78
:31295 q), which discloses acrylic vapor induced plasma treatment of carbon fibers. Such techniques also provide good-like coatings when yarn or tow of fibers are to be treated, since penetration into the innermost fibers is rather poor. Using an inductively coupled plasma (U.S. Pat. No. 3,776.829, ammonia and U.S. Pat.
, No. 634゜220, Oxygen), a method for producing functionalized carbon fibers that advantageously enhances the transverse rupture strength, tensile stress and shear strength of fibers in line with fibers in epoxy resin composites. No beneficial effect on the six-layer shear strength described is disclosed.

Unfortunately, the results achieved to date have generally been unsatisfactory and can otherwise be considered flawed, and/or there are no major improvements that are not easily reproducible. The drawbacks are believed to be lack of uniform film deposition or incomplete fiber entrainment. Furthermore, particularly with respect to the ion-blasting method, rough surface coatings are produced which do not endow the substrates made of yarn or tow with good handling properties. Coatings produced without bias of 1aIIi when ion-blated with 2-3 bundles are still rough and L) 11
11m<, the fibers are fused together. Accordingly, there is a need to improve the physical properties of composite materials to bring these properties closer to their theoretical values.

It is therefore a primary object of the present invention to provide an improved surface treatment for reinforcing means intended for end use in otherwise conventional composite assemblies. .

Another object of the invention is to provide an apparatus for carrying out such surface treatment.

Another object of the present invention is to provide an improved composite material assembly whose physical properties are increased or improved with respect to the prior art.

Yet another object of the present invention is to make substrates with enhanced surface properties from which composites are constructed due to their great compatibility as well as their great adhesion to the various matrix components. The object of the present invention is to provide a substrate which is eminently suitable for

In achieving these objectives, one feature of the invention is:
A substrate 1, e.g. in the form of a fiber, filament, fibril, film, ribbon, sheet, plate, block, etc., is electrically conductive, e.g. carbon, silicon, silicon carbide, etc., while the substrate is subjected to radio frequency excitation. ,
It consists in subjecting it to capacitively coupled plasma enhanced chemical vapor deposition. This differs from previous techniques in that the plasma is capacitively coupled and the substrate itself is biased at radio frequencies. This leads to a more efficient and more uniform surface coating even on the innermost fibers of a yarn or tow of bundles, for example of 3,000 to 12,000 fibers.

Additionally, in a preferred feature, the radio frequency input can be varied to produce a wide range of predetermined tensile stresses in order to match the properties to the matrix used. Yet another feature of the present invention is the use of the thus treated substrate as a reinforcing means for these post-treatment steps, including grafting with other monomers. The object of the present invention is to construct various composite assemblies in which the composite materials exhibit enhanced and improved physical and/or mechanical properties, such as tensile strength and/or flexural strength.

Other objects, features, and advantages of the present invention will be apparent to those skilled in the art from the detailed description of the invention that follows.

The present invention can be more easily understood by referring to the accompanying drawings: Plasma enhanced chemical vapor deposition is a very well known technique as exemplified in some of the above-mentioned documents. It is based on the equally well-known phenomenon of plasma polymerization of monomeric gases, which produces highly crosslinked thin films (approximately 1000 angstroms thick) on surfaces, and depending on the chemistry of the substrate, The coating can also be grafted onto the substrate. For plasma processing, a radio frequency oscillator can be coupled to an impedance matching box and power can be provided to the reaction vessel. Typically 10 to 1
Oo watts of power input.

Preferably it is used at a pressure substantially not exceeding about 5000 μl of mercury, most preferably in the range of 20 to 500 IL. The frequency of the power oscillator can vary widely, but typically ranges from about 0.5kHz to about 2500M
Within the range of Hz. Standard commercial equipment with 13.6 MHz oscillation is convenient. This process can be carried out batchwise or continuously.

In the present invention, supplying energy to the substrate is critical to the process to ensure radio frequency excitation. Unlike most methods of the prior art, in the present invention the plasma is capacitively coupled. With such features of the present invention, when multifilament fibers and tow yarns are to be coated,
A uniform and even film coating is provided even on the innermost fibers. Although not required, the pressure is substantially below atmospheric pressure, particularly preferably about 50 mercury columns.
It is also highly preferred to operate at pressures below 00 g, (microns);
It is still more preferable to operate within the range of 00#L;
Optimal results are achieved within the range of lO to lOO#L of mercury.

In accordance with the present invention and referring to FIG. 2, a basic plasma coating apparatus includes a radio frequency (RF) oscillator 2 (13,56 MHz, Materials Re
5earch Corp.), an impedance matching circuit 4, and a gas-tight container 6 (Pelger). Impedance matching circuit 4 allows optimal RF power transfer to the plasma. Mass flow -r-=tar 8 (Matheson) is reaction vessel 6
Measure the flow of gas into the. Seven liquids are held in a container IO. An inert gas, such as argon, is maintained in tank 12. Dry nitrogen is in tank 1
It is stored in 4.

The vacuum pump 16 is connected to the apparatus through a cold trap 18, which is assumed to be cooled with liquid nitrogen, for example. Any of a number of electrode arrangements can be used, such as those shown in Figures 2a, 2b and 2C, respectively, in which the substrate 20 is an electrode and is RF biased. Can be used.

The other electrode 22 is grounded. In all cases,
The geometry must be selected to provide uniform, non-directionally biased film deposition.

For example, if the electrode consists of a substrate 10 inches long or s, ooo or 12,000 wood carbon fiber tow (e.g. CELION 6 and 1
2, Ce1anese C.

rP, ), if the RF power input is in the range of 10 to 100 watts at a pressure of 30 to 400 liters of mercury, then the uniform Coatings are easily manufactured in which the innermost fibers are also coated.

The supply and take-up device can be easily assembled so that a continuous tow yarn can be conveyed through the plasma and coated according to the principles described above, where a continuous process is a preferred feature of the invention. A third suitable device
As shown in the figure. Here, the reaction zone container 24 is made of a quartz reaction tube. The RF oscillator and impedance matching circuit 26 is as shown in FIG. graphite fiber 2
The yarn yarn or tow yarn of 8 is placed in the vacuum introduction bushing 3.
2 and into the container tube 24 by passing it through one of the conductive rollers 30a and 30b. The other electrode is the RF grounded screen 3
Consists of 4. Gas is supplied into reaction vessel 24 through boats 36a and 36b, and means for evacuating the system include
It consists of a boat 38 connected to a vacuum pump (not shown).

To maintain airtightness, the coated tow yarn is removed through an outlet tube 38, which is also connected to a vacuum. Support plates 40a and 40b hold the device together and provide a means for grounding the grounded screen electrode 34. A supply roll 42 and a pick-up roll 44 are used to supply the fibers and collect the coated fibers. Optionally, means, such as a battery, may be interposed to render the substrate conductive, as shown in FIG. 2, device 3. This allows conductive substrate 20 to attract charged ions, providing enhanced film properties in some instances.

As illustrated by the examples, the materials fed to each reaction vessel can be of almost any desired type, whether elements, compounds, or mixtures thereof.
Produces a plasma enhanced chemical vapor deposition film. According to this procedure, in one aspect, at least one metal, metalloid or non-metallic element, such as antimony, tungsten, titanium, silicon and α-
Carbon can be coated onto the substrate. In another aspect, 5iXC1-X, Al2O3, CaO
1A I PO4# and silicon/nitrogen, silicon/
Carbon, silicon/carbon/oxygen, silicon/carbon/oxygen/
It will be shown that inorganic materials such as nitrogen and similar coatings can be uniformly coated. Such refractory coatings enhance wetting of the molten metal and impregnation of the fiber bundles. For example, AlPO4 on carbon is
Enhanced wetting by aluminum, see US Pat. No. 4,008,299. Such coatings are also useful in the assembly of ceramic composite materials because they provide oxidation resistance and control bonding to the ceramic matrix. These coatings are expected to also provide abrasion resistance, extending their use to commercial looms or braiding equipment. In yet another aspect, a substrate uniformly coated with a film of amorphous carbon having a high probability of active sites is subjected to a reaction while still under moderate vacuum prior to removal from the plasma apparatus. exposed to a monomer or polymer gas that reacts with the sexual locus,
The gas phase causes the polymer or polymer molecules to be grafted onto the amorphous carbon surface, and thereby
to sensualize. Such polymers or polymers exhibit maximum compatibility (c) for bonding to matrix materials.
compatibility).

For example, an amorphous carbon coating produced in a styrene plasma can be selectively functionalized with nitrogen-containing groups such as amides by briefly exposing the coating to an ammonia plasma before exposure to the surrounding atmosphere. Amorphous carbon coatings can also be functionalized with oxygen-containing groups by exposing the amorphous carbon coating to surrounding air.

Carbon coatings deposited in acrylic acid vapor result in free radical polymerization of acrylic acid on the fiber surface, which can be demonstrated by X-ray photoelectron spectroscopy.

Referring to FIGS. 1 and 18, continuous bundles of fibers used in core 50 in accordance with the present invention are commercially available from a number of sources. For example, suitable carbon fiber yarns are available from Hereules Company;
Hitco, Great Lakes Carbon
Company, AVCO Company and similar suppliers in the United States, and internationally. All are generally manufactured by the procedure described in US Pat. No. 3,677,705. The fibers can be long and continuous, or they can be short, e.g.
The length shall be 5cm.

The core can also contain metals, preferably as a surface layer, particularly preferably nickel, copper, lead, gold, silver,
It can be included as an electroplated metal layer containing mixtures of these and the like. These are preferably European Patent Application No. 8310119 by the applicant
5.2 (September 21, 1983).

Membrane 52 consists of any metal, metalloid or non-metal, element or compound, or mixture thereof, deposited onto the core by plasma enhanced chemical vapor deposition. As shown in the operational examples, such membranes can be applied with two or even more layers, and the membranes can be of the same type or of different types.

In other embodiments (not shown), the core can consist of a plate-like substrate and an adhesive or coating can be applied onto the membrane, for which the adhesive continuous phase acts as a matrix. do. To illustrate the beneficial influence of each membrane on such substrates, the platelets can be coated with a thin layer of adhesive, for example consisting of a thin layer of bisphenol A diepoxide and diethylene triamine. resin for 16 hours and then at 80
Cure for 2 hours at 0.degree. C. provides a significant increase in bond strength due to the presence of the surface film of the present invention.

Fibers coated with the membranes of the present invention can be assembled by conventional means into a composite material as shown in FIG. ceramic,
The matrix, for example glass, is reinforced thanks to the presence of a membrane-coated fibrous core 50.

For the production of polymeric matrix fiber-reinforced composite materials, the applicant's European Patent Application No. 83101196
．． Any method known in the art may be used, such as the method described in J.D. 0 (October 5, 1983). The polymeric material can be applied onto a membrane-coated reinforcement in the form of fibers, yarns or tows, woven, braided or knitted fabrics, non-woven sheets, shredded fibers, etc. Coating, melt blending, solvent blending, etc. may be performed. Suitable resins include polyesters, polyethers, polycarbonates, epoxides, phenolic resins, epoxy novolacs, epoxy polyurethanes, urea-type resins, phenol formaldehyde resins,
Melamine resin, melamine thiourea resin, urea-aldehyde resin, alkyd resin polysulfide resin, vinyl organic prepolymer, polyfunctional vinyl ether, cyclic ether, cyclic ester, polycarbonate conistere, polycarbonate cosilicone, polyether ester, polyimide, polyamide , polyesterimide, polyamideimide, polyetherimide and polyvinyl chloride, mixtures of any of the above, and the like. Polymeric materials can be present alone or in combination with copolymers, and polymer blends can also be used. Polymeric materials, when combined with the coated reinforcements of the present invention, can be cured by heat or light, alone or in combination with catalysts, accelerators, cross-linking agents, etc., to form materials, protective coatings, sports materials, office equipment, etc. can be converted to form parts suitable for end uses such as crosslinking, television cabinets, etc. The amount of reinforcement used is conventional, but preferably the reinforcement will constitute at least about 40% by volume of the composite.

Carbon and Graphite Fib is used to make ceramic matrix reinforced composite materials.
ers, Marshall 5itt 1g1i', N
oyes Data Corp, 1980. pp,
Any method known in the art may be used, such as the method described in No. 263-269. Membrane coated fiber 1
For example, at least 40% by volume of glass, cement.

and ceramics such as refractory compounds such as niobium carbide or tantalum carbide. Thermal shock resistance and reduced brittleness are two properties that are advantageously affected by strengthening ceramics in this way.

The invention is illustrated by the following non-limiting examples.

The basic plasma coating apparatus is schematically represented in FIG.
5earch Corp.), an impedance matching circuit, and a Pelger or tubular reaction vessel. The impedance matching circuit allows for optimal RF power transfer to the plasma. The flow of gas into the reaction vessel is controlled by MatheS
It was measured using a mass flow monitor on.

The electrode arrangement used is shown in Figures 2a-c,
The actual placement is specified within each example.

The RF power input to the reaction vessel was typically in the range of lO to 100 Watts at a pressure of 30 to 400 IL of mercury. Most embodiments are based on Ce1ion 6, 6
The test was carried out on a 10 inch length of 000 carbon fiber tow yarn. However, for continuous processing, a feed and take-off whisker device was assembled to transport the tow yarn continuously through the plasma with a total capacity of lOm.

The surface effects of plasma-assisted chemical vapor deposition (c v n) were evaluated using X-ray photoelectron spectroscopy (XPS') and scanning electron microscopy on both treated and untreated fiber samples.

Real Ju11 The apparatus of Figure 2 was used with the electrode arrangement shown.

RF small output 20 watts, total pressure 5bC1, steam 40
The background pressure of the zero reaction vessel was 10 mTorr at mTorr (404). After 15 minutes of exposure, a metallic-looking coating of antimony approximately 1000 angstroms thick was obtained on each fiber of the bundle. There was no non-uniform, directionally biased nQ deposition.

The apparatus of Figure 2 was used with the electrode arrangement shown. RF small output 10 watts, total pressure 100
mTorr. The background pressure in the reaction vessel was lOmTorr. After 15 minutes of exposure, approximately 50
A fiber uniformly coated with a thin film of titanium with a thickness of 0.00 angstroms was obtained.

The apparatus of Figure 2 was used with the electrode arrangement shown. RF specific output is 20 Watts, total pressure is 100mTor
The background pressure of the 0 reaction vessel is 1Om
0 reaction vessel pressure which was Torr to 20mTo in wpa
The 0 reaction vessel heated to 20 mTorr was then heated to 20 mTorr with H2.
The pressure was increased from 100 to roomTorr. After 10 minutes, a coating of tungsten was deposited and was about 5000 Angstroms thick.

X5 Yul! ! J, the apparatus of Figure 2 was used with the electrode arrangement shown. The RF specific output was set to 25 watts. The total pressure was 40 mTorr (SiH, +Ar). The background pressure of the system was 1 OmTorr. The reaction vessel pressure was increased to 30 mTorr with Ar, then SiH
, the pressure was increased to 40 mTorr. After 5 minutes, about 1 river (
A flat coating of Si 10,000 angstroms thick was deposited onto the fibers.

(CΣ, The apparatus of Figure 2 was used with the electrode arrangement shown. The RF specific power was 50 Watts. The total pressure was 60 mT.
It was set as orr. The background pressure is lOmTor
The 0 reaction vessel pressure, which was r, was reduced to 60 mTo with styrene vapor.
Raised it to rr. After 3 minutes, a uniform thin film of α-carbon about two hundred angstroms thick was deposited on the fibers.

The device was used with the electrode arrangement shown. The RF specific output was 20 Watts, and the total pressure was about 56-58 mTorr. The CH4 flow rate is 1.7 standard cubic centimeters per minute (
SCCM), and the SiH4 flow rate was 1.73 CCM. The Ar flow rate was 21° and 23 CCM. After 1 hour, approximately 1500 angstroms of carbon-silicon film was uniformly coated onto the fibers.

The apparatus of Figure 2 was used with the electrode arrangement shown.

The RF specific output was 40 Watts, and the total pressure was 26 mTorr. The SiH4 flow rate was 1.8 SCCM. C2H, flow rate was 11-753CC. After 1 hour, a carbon-silicon film approximately 14 mm thick was uniformly coated onto the fibers.

! Kei 1J SiCI NHBIN to silicon - Nitrogen (SiN) evaporation.

The apparatus of Figure 2 was used with the electrode arrangement shown.

The RF specific output was 20 Watts, and the total pressure was about 40 mTorr. The NH3 flow rate was between 1 and O3CC. The N2 flow rate was 1.5 secM.

The 5iC14 flow rate was 0.73 CCM. After 45 minutes, the carbon fibers were thinly and uniformly coated with a silicon-nitrogen film approximately 500 angstroms thick.

vinegar. The apparatus of Figure 2 was used with the electrode arrangement shown. The RF specific output was set to 20 watts. Total pressure is 60mTor
It was set as r. The air pressure was 20 mTorr. Si
The system was brought to 60 mTorr by flowing H4, CH, and argon gases at a first-order flow rate: SiH4
, 1,7 scCM; CH4, 1,7 scCM; and argon 21.23 CCM, after 1 hour, about 6000-7
A uniform thin film of 0.000 angstroms thickness was deposited with the following elemental crudes: C,
22.4 at.%; 0.44.5 at.%, N, 7.4 at.%; and Si, 25.8 at.%.

Shito Jingtu 0-12 The general procedure of Example 6 was repeated, replacing the styrene plasma with a butane and acrylic acid vapor plasma.

In all cases, amorphous carbon (α-carbon) films were deposited.

EXAMPLE 1: Following the procedure of Example 6, but substituting an acrylic acid plasma for the styrene plasma, and subsequently exposing the amorphous alpha-carbon film coated fibers to laboratory air. A significantly increased amount of surface oxygen (according to XPS) and a change in the distribution of functionality (more 10=0 groups than on the untreated fiber surface) are obtained. xPS analysis of the film yielded the following compositions: O, a, at %; o, 2° 1s 1s 26 atomic %; c, 65.58 atomic %; s C, 16,0 atomic %; and C. ,7,3is ls 6 atom%.

If immediately after α-carbon film deposition, the film is first exposed to acrylic acid monomer vapor and then (after evacuation)
If this procedure were repeated outside the entourage exposed to air, a more selectively functionalized surface would be obtained, with a marked increase in the amount of C-O groups and a decrease in the amount of C=0 groups. It happens.

XPS analysis of the film gave the following results: 0
．． 11.16 atomic %: 0.31 S I S .

15 atom%; c, 58.0 atom%; 01s.

s 21.17 atom%; and C, 6,52 atom s %.

! Falling down the cliff 1:”1 The apparatus of Figure 2 was used with the electrode arrangement shown.

The low RF output was set at 25 watts. The vacuum system was first filled with argon to a pressure of 201 L, then filled with styrene vapor to a pressure of 401 L.
Filled up to L. After 10 minutes, the α-carbon film co-coated fibers were exposed to air. The amount of O was 5.3 at% and C1ss was 94.7 at%. The above method was repeated, except that instead of air, one α-carbon film was used.
Immediately exposed to ammonia gas for 15 minutes at 000μ.

The film was analyzed by XPS analysis and showed traces of nitrogen: 0. 6°s 25 at%; c, 92.4 at%; and S N, 1.32 at%; repeating this procedure, but using post-treatment in ammonia plasma (
The N10 ratio of ~1 in the analyzed membranes indicated that the nitrogen was present in the form of NH, groups (at 20 watts RF power for 2 minutes at ammonia pressure of 500 min). According to the analysis, 0. 8.11 atomic %, C, 83.4 atomic %; and NIs' 8.44 atomic %. In all cases, the coating was approximately 1000 angstroms thick.

Nickel-coated carbon Silicon from SiH to The apparatus of Figure 2 was used with the electrode arrangement shown.

The substrate is based on the applicant's above-mentioned European Patent Application No. 831011.
It consisted of 6000 carbon fiber tow yarn coated with 50% by weight nickel by the electroplating method described in Example 1 of 95.2. RF small output 3
It was set to 0 watts. The total pressure was 33 JL of mercury. SiH
The flow rate in No. 4 was 3.55 CCM. 10 minutes later, about 10,
A flat coating of Si, 1,000 angstroms thick, was deposited onto a piece of nickel-coated carbon fiber.

A pyrolytic graphite plate was placed in the apparatus shown in Figure 2 and a low RF power bias of 40 watts was applied. The zero reaction vessel, whose total pressure was 80 mTorr, was evacuated to 4 mTorr, then backfilled with H2 to 42 mTorr, and further filled to Al(CH*)si' 80 mTorr. The deposition time was 30 minutes. A uniform film is deposited on the plate,
This one was made of AlOH, and in the formula x
y y X is 2 or less, and y is 3 or less. After heat treatment to ˜1000° C., the film produced stoichiometric Al2O5.

Sway m An array is made from aligned graphite yarn threads coated with a selectively functionalized alpha-carbon film by the procedure of Example 17. These are impregnated with a thermosetting composition containing an epoxy resin and a polyamino curing agent.

The array was assembled into a three-dimensional shape and the epoxy resin was heat cured, with the resin being the matrix and the film-coated graphite yarns being the reinforcing phase (approximately 40
~50% by volume). This composite material exhibits improved short beam shear strength compared to that made with uncoated l/~ graphite yarn yarn according to the present invention.

A membrane-coated fiber tow yarn made of carbon and coated with a carbon-silicon membrane according to the procedure of Example 7 was fabricated into a ceramic matrix by fusing powdered glass to the reinforcement. Converted into a composite material (approximately 40% by volume of reinforcement), this composite material exhibits better stability than those reinforced with fibers not coated with a membrane according to the invention, when exposed to heat in an oxidizing atmosphere. Shown after the cycle.

Example composite articles containing plasma-coated fibers are useful for support beams in space structures, lightweight bridges, internal combustion engine components for gas turbines and internal combustion equipment for aircraft, where lightweight and stiff components are required. It finds use in applications such as , aerial vehicles, etc.

The patents and publications mentioned above are herein incorporated by reference. In view of the above detailed description, many variations of the invention will occur to those skilled in the art. Composite materials can also be produced consisting of reinforced epoxy or polyimide polymer matrices. and Examples 1-6 and 8-17
Composite materials of other ceramics and cements reinforced with fibers coated with the procedure can also be produced. Furthermore, the radio frequency power can be varied to produce membranes with predetermined tensile stresses.

Higher power results in higher tensile stress. Wattages in the range of 10 to 100 provide film tensile stresses in the range of 30°, ooo to 30.000.000 pounds per square inch. A calibration chart can easily be created to convert the output to final tensile stress. All such variations are intended to be within the full intended scope of the invention as defined in the following claims.

[Brief explanation of drawings]

The accompanying drawings show a fiber coated with a membrane according to the invention, an apparatus for carrying out the method of the invention and its electrode arrangement, 1 an apparatus for carrying out the process of the invention continuously, and a fiber reinforced with a membrane coated fiber of the invention. represents a matrix composite material. This is a schematic drawing. FIG. 1 is a cross-sectional view of a film-coated fiber of the present invention. FIG. 1a is a longitudinal cross-sectional view of a film-coated fiber according to the invention. FIG. 2 shows an apparatus for carrying out the method of the invention. Figures 2a, 2b and 20 are illustrations of electrode arrangements suitable for use in the apparatus shown in the ts2 diagram for carrying out the method of the invention. FIG. 3 is a schematic diagram of an apparatus for continuously carrying out the plasma-assisted chemical vapor deposition method of the present invention. Figure 4 shows the film-coated m#I of the present invention.
FIG. 2 is a partial cross-sectional view of a reinforced matrix composite. Patent applicant American Cyanamid Campa FIG
, 2a FIG, 2c FIG, 2b FjG, 4 Continued from page 1 Priority claim ■198 disease April 16 [phase] United States (U.S.
) [Co.] 5902520198 Group March 16 [Phase] United States (US) [Phase] 5902530198 Group March 16 [Phase] United States (US) [Co.] 5902540 Inventors Charles Bergin United States of America Gu Bean Jr. Hall Road, Michigan 48462 Ortonville Grain 500 Procedural Amendment (Method) % Formula % 1. Display of the case Showa 6D Patent Application No. 48450 2. Title of the invention 3. Relationship with the children's case making the amendment Patent applicant 4. Agent Address: 107 Phone: 685-2256

Claims (1)

Claims: 1. at least a radio frequency conductive core comprising carbon and at least one other non-metal deposited on the core by plasma enhanced chemical vapor deposition while exciting the core with radio frequencies; A coated substrate consisting of a thin, uniform, and firmly adhered organic film. 2. The coating of claim 1, wherein the organic film is deposited on the core with applied radio frequency power selected to produce a film with a predetermined tensile stress. substrate. 3. The coated substrate of claim 1, wherein the organic film is functionalized. 4. The functionalized organic film is deposited on the core with applied radio frequency power selected to produce a film with a predetermined tensile stress. Coated substrates as described in Section. 5. A claim comprising: the applied radio frequency power is in the range of about 10 to about 1000 watts; and the membrane tensile stress is in the range of about 300,000 to about 30,00 degrees, ooo pounds per square inch. The coated substrate according to claim 2. 6. A patent claim comprising: the applied radio frequency power is in the range of about lO to about 1000 watts; and the membrane tensile stress is in the range of about 300,000 to about 30,00 o, ooo bond per square inch. 4. The coated substrate according to claim 4. 7. The coated substrate of claim 1, wherein the film is deposited on the core at a vapor pressure of substantially no more than 5.000% mercury. 8. The membrane has a mercury content of about 20 to about 500. 8. The coated substrate of claim 7, wherein the coated substrate is deposited onto the core at a vapor pressure in the range of . 9. The thickness of the film is about 50 to about io, o. 0 angstroms. A coated substrate according to claim 1. 10. The coated substrate of claim 9, wherein the film thickness is within the range of about 200 to about 50,000 Angstroms.