USH641H - Process for making coatings on graphite using intercalated species - Google Patents
Process for making coatings on graphite using intercalated species Download PDFInfo
- Publication number
- USH641H USH641H US07/220,135 US22013588A USH641H US H641 H USH641 H US H641H US 22013588 A US22013588 A US 22013588A US H641 H USH641 H US H641H
- Authority
- US
- United States
- Prior art keywords
- fibers
- graphite
- metal
- carbon
- carbon fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 17
- 229910002804 graphite Inorganic materials 0.000 title abstract description 18
- 239000010439 graphite Substances 0.000 title abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 32
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 10
- 238000009831 deintercalation Methods 0.000 claims abstract description 8
- 238000009830 intercalation Methods 0.000 claims abstract description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 20
- 239000004917 carbon fiber Substances 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/123—Oxides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
Definitions
- This application relates to two companion applications titled PREPARATION OF METAL OXIDE FIBERS FROM INTERCALATED GRAPHITE FIBERS, U. S. application Ser. No. 07/217991, and PRODUCTION OF 10 MICRON DIAMETER HOLLOW ALUMINA FIBERS, U.S. application Ser. No. 07/220/36, both filed on the same date as this application and hereby incorporated by reference as if fully rewritten herein.
- the invention relates generally to a process for coating fibers, and more specifically to a process for making metal oxide coatings on graphitic carbon fibers and other graphitic material.
- Carbon fibers are increasingly valuable as reinforcing materials in a variety of composite structural materials.
- a common problem with carbon fibers is that the carbon is very susceptible to oxidation especially on graphite basal plane edges, which seriously impairs the desired physical and mechanical properties of the carbon fibers.
- the coating material comes from within the fiber and deposits initially at the graphite layer plane edges, thereby forming preferentially at the locations where oxidation is most rapid.
- the present invention provides a novel process for depositing a metal oxide coating on carbon-graphite fibers.
- the unique discovery of the present invention is that intercalating, and then deintercalating, the fibers will form a coating on the fiber surfaces.
- the invention is directed to a method for coating a graphitic carbon fiber, comprising the steps of intercalating a metal chloride into the fiber and then deintercalating the chlorine from the fiber by hydrolysis to form a metal oxide on the fiber surface.
- the hydrolysis should be performed at progressively higher temperatures over a range of about 100° C. to a temperature at which oxidation of the graphite itself occurs at a faster rate than the hydrolysis reaction.
- the invention also includes using aluminum chloride as the metal chloride and aluminum oxide as the metal oxide.
- the invention also includes a method for coating a graphitic carbon fiber, comprising intercalating a metal-bearing species into the carbon fiber and then deintercalating the carbon fiber to form a metal-bearing ceramic species on the fiber surface.
- the invention further includes the metal oxide and metal species coated carbon fibers made according to the disclosed methods.
- a metal chloride is first intercalated into carbon-graphite fibers by standard techniques well known in the art.
- Carbon-graphite fibers, or simply graphite fibers are carbon fibers where the carbon is primarily in graphite form.
- Such graphitic carbon fibers, and other graphitic carbon based materials can be prepared or obtained in varying degrees of graphitization.
- the present invention, and the cross-referenced companion applications, will work with any carbon fiber or other carbon material displaying a graphitic character to a degree sufficient to provide layer planes between which intercalation may take place.
- AlCl 3 intercalated aluminum chloride
- tows of Union Carbide P-100 graphite fibers the fibers are heated at ⁇ 300° C. in air to remove any sizing.
- the fibers are then placed inside a Pyrex tube to which aluminum chloride and chlorine gas (Cl 2 ) are added.
- the Cl 2 is frozen in the tube and the tube sealed under vacuum.
- the sample is next heated to generate a sufficient vapor pressure of aluminum chloride.
- the tube is cooled and opened in a drybox.
- the added AlCl3 and Cl 2 will generally be sufficient to produce C n + AlCl 4 - (n ⁇ 36) in-between the crystalline layers comprising the graphite fibers.
- the intercalated fibers are next hydrolyzed by bubbling nitrogen gas through water and then over the intercalated fibers at very slowly increasing temperatures from 100° to below 600° C. in steps of abouI 50 to 100 degrees. Within a week at 100° C., white material representing the metal oxide will form on the fiber surfaces.
- the disclosed process successfully demonstrates the use of intercalating into, and then deintercalating from, fibers to form a coating or surface layer on the fibers. Although the disclosed use is specialized, it will find application in other areas where application of surface coatings is required. Extension of the underlying methodology of the disclosed processes using different intercalants and different deintercalation reactions will provide other coatings.
- Other metal-bearing species such as metal halides or metal nitrates, can be intercalated into graphite or other graphitic material and then deintercalated by hydrolysis, or by processes other than hydrolysis.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Carbon-graphite fibers are coated with a protective metal oxide coating by intercalating the fibers with a metal chloride and then deintercalating the chlorine by hydrolysis to form a metal oxide over the fibers. An example using aluminum chloride to form an aluminum oxide coating is described.
Description
The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
This application relates to two companion applications titled PREPARATION OF METAL OXIDE FIBERS FROM INTERCALATED GRAPHITE FIBERS, U. S. application Ser. No. 07/217991, and PRODUCTION OF 10 MICRON DIAMETER HOLLOW ALUMINA FIBERS, U.S. application Ser. No. 07/220/36, both filed on the same date as this application and hereby incorporated by reference as if fully rewritten herein.
The invention relates generally to a process for coating fibers, and more specifically to a process for making metal oxide coatings on graphitic carbon fibers and other graphitic material.
Carbon fibers, particularly carbon-graphite fibers, are increasingly valuable as reinforcing materials in a variety of composite structural materials. A common problem with carbon fibers is that the carbon is very susceptible to oxidation especially on graphite basal plane edges, which seriously impairs the desired physical and mechanical properties of the carbon fibers.
The prior art has investigated a very large variety of coating processes and other methods for making carbon fibers more oxidatiopn resistant. While much valuable work has been done, additional improvements are still needed.
It is, therefore, a principal object of the present invention to provide a process for depositing metal oxide coatings on the surface of graphite fibers and other graphitic materials.
It is an advantage of the present invention that the coating material comes from within the fiber and deposits initially at the graphite layer plane edges, thereby forming preferentially at the locations where oxidation is most rapid.
It is another advantage of the present invention that the process is simple to understand and to perform.
In accordance with the foregoing principles, advantages and objects, the present invention provides a novel process for depositing a metal oxide coating on carbon-graphite fibers. The unique discovery of the present invention is that intercalating, and then deintercalating, the fibers will form a coating on the fiber surfaces.
Accordingly, the invention is directed to a method for coating a graphitic carbon fiber, comprising the steps of intercalating a metal chloride into the fiber and then deintercalating the chlorine from the fiber by hydrolysis to form a metal oxide on the fiber surface.
The hydrolysis should be performed at progressively higher temperatures over a range of about 100° C. to a temperature at which oxidation of the graphite itself occurs at a faster rate than the hydrolysis reaction.
The invention also includes using aluminum chloride as the metal chloride and aluminum oxide as the metal oxide.
The invention also includes a method for coating a graphitic carbon fiber, comprising intercalating a metal-bearing species into the carbon fiber and then deintercalating the carbon fiber to form a metal-bearing ceramic species on the fiber surface.
The invention further includes the metal oxide and metal species coated carbon fibers made according to the disclosed methods.
A metal chloride is first intercalated into carbon-graphite fibers by standard techniques well known in the art. Carbon-graphite fibers, or simply graphite fibers, are carbon fibers where the carbon is primarily in graphite form. Such graphitic carbon fibers, and other graphitic carbon based materials, can be prepared or obtained in varying degrees of graphitization. The present invention, and the cross-referenced companion applications, will work with any carbon fiber or other carbon material displaying a graphitic character to a degree sufficient to provide layer planes between which intercalation may take place.
For example, to intercalated aluminum chloride (AlCl3) into tows of Union Carbide P-100 graphite fibers (approximately 2000 graphite fibers in a continuous tow), the fibers are heated at ˜300° C. in air to remove any sizing. The fibers are then placed inside a Pyrex tube to which aluminum chloride and chlorine gas (Cl2) are added. The Cl2 is frozen in the tube and the tube sealed under vacuum. The sample is next heated to generate a sufficient vapor pressure of aluminum chloride. After 1-3 days, the tube is cooled and opened in a drybox. The added AlCl3 and Cl2 will generally be sufficient to produce Cn + AlCl4 - (n˜36) in-between the crystalline layers comprising the graphite fibers.
The intercalated fibers are next hydrolyzed by bubbling nitrogen gas through water and then over the intercalated fibers at very slowly increasing temperatures from 100° to below 600° C. in steps of abouI 50 to 100 degrees. Within a week at 100° C., white material representing the metal oxide will form on the fiber surfaces.
In this hydrolysis of Cn + AlCl4 -, the intercalated AlCl4 - should act like AlCl3 and form AlOCl at low temperatures as shown in the equation below. AlOOH should then form fairly readily at temperatures above 400° C., and Al2 O3 form at temperatures near and above 600° C. ##STR1##
Extreme care should be taken to slowly increase the temperature at which hydrolysis takes place because the graphite will slowly begin to oxidize at about 600° C. The hydrolysis should preferably be performed at temperatures at which the hydrolysis reaction occurs at a faster rate than oxidation of the graphite.
The disclosed process successfully demonstrates the use of intercalating into, and then deintercalating from, fibers to form a coating or surface layer on the fibers. Although the disclosed use is specialized, it will find application in other areas where application of surface coatings is required. Extension of the underlying methodology of the disclosed processes using different intercalants and different deintercalation reactions will provide other coatings. Other metal-bearing species, such as metal halides or metal nitrates, can be intercalated into graphite or other graphitic material and then deintercalated by hydrolysis, or by processes other than hydrolysis.
Those with skill in the art will see that the disclosed method of making coatings will work as well on other carbon materials such as woven carbon fabrics and bulk graphitic materials.
It is understood that other modifications to the invention as described may be made, as might occur to one with skill in the field of the invention. Therefore, all embodiments contemplated have not been shown in complete detail. Other embodiments may be developed without departing from the spirit of the invention or from the scope of the claims.
Claims (4)
1. A method for coating a graphitic carbon fiber, comprising the steps of:
(a) intercalating a metal chloride into the carbon fiber; and,
(b) deintercalating the chlorine from the carbon fiber by hydrolysis to form a metal oxide on the fiber surface.
2. The method according to claim 1, wherein the hydrolysis is performed at progressively higher temperatures over the range of about 100° C. to temperature at which oxidation of the carbon occurs at a faster rate than the hydrolysis reaction.
3. The method according to claim 1, wherein the metal chloride is aluminum chloride and the metal oxide is aluminum oxide.
4. A method for coating a graphitic carbon fiber, comprising:
(a) intercalating a metal-bearing species into the carbon fiber; and.
(b) deintercalating from the carbon fiber to form a metal-bearing species ceramic on the fiber surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/220,135 USH641H (en) | 1988-07-05 | 1988-07-05 | Process for making coatings on graphite using intercalated species |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/220,135 USH641H (en) | 1988-07-05 | 1988-07-05 | Process for making coatings on graphite using intercalated species |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH641H true USH641H (en) | 1989-06-06 |
Family
ID=22822218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/220,135 Abandoned USH641H (en) | 1988-07-05 | 1988-07-05 | Process for making coatings on graphite using intercalated species |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USH641H (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073412A (en) * | 1990-11-02 | 1991-12-17 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Method of intercalating large quantities of fibrous structures |
| US5225171A (en) * | 1990-11-02 | 1993-07-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration | Apparatus for intercalating large quantities of fibrous structures |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4102937A (en) | 1976-12-03 | 1978-07-25 | Phillips Petroleum Company | Cycloparaffin isomerization using a catalytically active aluminum halide intercalated in graphite |
| US4267211A (en) | 1978-11-13 | 1981-05-12 | The Foundation: The Research Institute For Special Inorganic Materials | Process for producing corrosion-, heat- and oxidation-resistant shaped article |
| US4267210A (en) | 1978-07-28 | 1981-05-12 | The Foundation: The Research Institute For Special Inorganic Materials | Method for producing corrosion-, heat- and oxidation-resistant materials |
| US4440571A (en) | 1981-07-10 | 1984-04-03 | Nippon Carbon Co., Ltd. | Process for the surface treatment of inorganic fibers for reinforcing titanium or nickel and product |
| US4605588A (en) | 1985-03-14 | 1986-08-12 | The Boeing Company | Barrier coated ceramic fiber and coating method |
| US4642271A (en) | 1985-02-11 | 1987-02-10 | The United States Of America As Represented By The Secretary Of The Navy | BN coating of ceramic fibers for ceramic fiber composites |
-
1988
- 1988-07-05 US US07/220,135 patent/USH641H/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4102937A (en) | 1976-12-03 | 1978-07-25 | Phillips Petroleum Company | Cycloparaffin isomerization using a catalytically active aluminum halide intercalated in graphite |
| US4267210A (en) | 1978-07-28 | 1981-05-12 | The Foundation: The Research Institute For Special Inorganic Materials | Method for producing corrosion-, heat- and oxidation-resistant materials |
| US4267211A (en) | 1978-11-13 | 1981-05-12 | The Foundation: The Research Institute For Special Inorganic Materials | Process for producing corrosion-, heat- and oxidation-resistant shaped article |
| US4440571A (en) | 1981-07-10 | 1984-04-03 | Nippon Carbon Co., Ltd. | Process for the surface treatment of inorganic fibers for reinforcing titanium or nickel and product |
| US4642271A (en) | 1985-02-11 | 1987-02-10 | The United States Of America As Represented By The Secretary Of The Navy | BN coating of ceramic fibers for ceramic fiber composites |
| US4605588A (en) | 1985-03-14 | 1986-08-12 | The Boeing Company | Barrier coated ceramic fiber and coating method |
Non-Patent Citations (4)
| Title |
|---|
| "Deintercalation Reactions to Form Ceramic Coatings on Graphite Fibers" B. W. McQuillan and G. H. Reynolds, Abstract, Boston, Mass., Dec. 1986. |
| "Growth of Alumina Fibers from Intercalated Graphite Precursor Fibers" B. W. McQuillan and G. H. Reynolds, Abstract, San Diego, Calif., Jan. 1987. |
| "Preparation of Ceramic Fibers by Conversion Intercalated Graphite Fibers" B. W. McQuillan and G. H. Reynolds, Abstract, Pittsburgh, Pa., Apr. 1987. |
| "Synthesis of Refractory Ceramic Fibers from Intercalated Graphite Fiber Precursors," B. W. McQuillan and G. H. Reynolds, Abstract, Anaheim, Calif., Apr. 87. |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073412A (en) * | 1990-11-02 | 1991-12-17 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Method of intercalating large quantities of fibrous structures |
| US5225171A (en) * | 1990-11-02 | 1993-07-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration | Apparatus for intercalating large quantities of fibrous structures |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: UNITED STATES OF AMERICA, THE, AS REPRESENTED BY T Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. SUBJECT TO CONDITIONS RECITED;ASSIGNORS:GA TECHNOLOGIES INC.;MC QUILLAN, BARRY W.;REYNOLDS, GEORGE H.;REEL/FRAME:004974/0065;SIGNING DATES FROM 19880624 TO 19880629 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |