US3657082A - Treatment of fibrous materials - Google Patents
Treatment of fibrous materials Download PDFInfo
- Publication number
- US3657082A US3657082A US787558A US3657082DA US3657082A US 3657082 A US3657082 A US 3657082A US 787558 A US787558 A US 787558A US 3657082D A US3657082D A US 3657082DA US 3657082 A US3657082 A US 3657082A
- Authority
- US
- United States
- Prior art keywords
- carbon fibers
- treatment
- fibers
- fibrous materials
- order
- 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.)
- Expired - Lifetime
Links
- 238000011282 treatment Methods 0.000 title description 9
- 239000002657 fibrous material Substances 0.000 title description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 20
- 239000004917 carbon fiber Substances 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 8
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 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
- D01F11/121—Halogen, halogenic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- 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
- D01F11/122—Oxygen, oxygen-generating compounds
-
- 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
- D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
Definitions
- ABSTRACT In order to improve the surface characteristics of carbon fibers, e.g. their adhesion to a resin matrix, they are treated by immersion in an aqueous oxidising agent, e.g. a hypochlorite.
- an aqueous oxidising agent e.g. a hypochlorite.
- the present invention relates to the treatment of fibrous material and more particularly to the treatment of carbon or graphite fibers.
- carbon fibers may be made by taking fibers of an organic material, such as polyacrylonitrile, and subjecting them to high temperatures. Very often the heat treatment is effected in several steps in different atmospheres and the final temperature may be in the range l,500 to 2,600 C so that the fibers may be at least partially graphitized.
- the term carbon fibers is used inclusively hereinafter.
- These carbon fibers may have many uses, but one use is to reinforce a matrix, more particularly a matrix of plastics material, in order to produce a reinforced or laminated material in rather a similar way to that in which glass fiber is used to reinforce plastics material.
- One difficulty that has been found is that poor adhesion may occur between the carbon fibers and the matrix which leads to reduced mechanical strength of the composite.
- carbon fibers are surface treated by immersion in an aqueous oxidizing agent.
- the aqueous oxidizing agent is a hypochlorite solution containing available chlorine.
- hypochlorite solution One very desirable way of obtaining the hypochlorite solution is to generate it by electrolysis of a chloride solution using the carbon fibers as one electrode.
- the fibers were then placed in a bath containing 5 percent by weight of sodium chloride and 0.25 percent by weight of sodium hydroxide in water.
- the fibers were connected to the anode and were at the same time subjected to ultrasonic agitation at 13 kHz.
- a copper cathode was also inserted in the bath and current was passed between the cathode and anode at a current density of 2 amps per square inch of carbon fiber surface and at a voltage of 12 volts. After treatments for 5 minutes in this bath (which generated free chlorine) the carbon fibers were removed, rinsed in water and dried.
- the carbon fibers were then incorporated into an epoxide resin matrix in the proportion of 55 percent by volume and the resulting composite was tested in a 3 point bend test on a 1 inch beam.
- the interlaminar shear strength of the composite was 6,275 p.s.i. which compares with a strength of 2,000 to 3,000 p.s.i. for a similar laminate made from untreated fibers.
- a method of surface treating carbon fibers comprising generating a hypochlorite solution containing available chlorine by electrolysis of an aqueous chloride solution using carbon fibers as the anode.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
In order to improve the surface characteristics of carbon fibers, e.g. their adhesion to a resin matrix, they are treated by immersion in an aqueous oxidising agent, e.g. a hypochlorite.
Description
United States Patent Wells etal.
[ 3,657,082 [451 Apr. 18, 1972 TREATMENT OF FIBROUS MATERIALS Henry Wells, Wantage; William James Colclough, Didcot, both of England United Kingdom Atomic Energy Authority, London, England Filed: Dec. 27, 1968 Appl. No.: 787,558
Inventors:
Assignee:
Foreign Application Priority Data Jan. 3, 1968 Great Britain ..525/68 U.S. Cl ..=204/130 Int. Cl. ..C0ld 7/34 Field ofSearch ..204/130, 95, 173, 132, 128,
Primary ExaminerJ0hn H. Mack Assistant ExaminerR. L. Andrews Attorney-Larson, Taylor and Hinds [5 7] ABSTRACT In order to improve the surface characteristics of carbon fibers, e.g. their adhesion to a resin matrix, they are treated by immersion in an aqueous oxidising agent, e.g. a hypochlorite.
2 Claims, No Drawings TREATMENT OF FIBROUS MATERIALS The present invention relates to the treatment of fibrous material and more particularly to the treatment of carbon or graphite fibers.
It will be known that carbon fibers may be made by taking fibers of an organic material, such as polyacrylonitrile, and subjecting them to high temperatures. Very often the heat treatment is effected in several steps in different atmospheres and the final temperature may be in the range l,500 to 2,600 C so that the fibers may be at least partially graphitized. However, for convenience, the term carbon fibers is used inclusively hereinafter.
These carbon fibers may have many uses, but one use is to reinforce a matrix, more particularly a matrix of plastics material, in order to produce a reinforced or laminated material in rather a similar way to that in which glass fiber is used to reinforce plastics material. One difficulty that has been found is that poor adhesion may occur between the carbon fibers and the matrix which leads to reduced mechanical strength of the composite.
In order to overcome the above difficulty, it has hitherto been proposed to apply a surface oxidation treatment to the carbon fibers after production, but we have found that if this treatment is carried out in air or oxygen it is extremely liable to cause runaway oxidation and/or pitting, either of which materially weaken the carbon fibers. It has therefore been proposed in our co-pending British application Ser. No. 524/68 of even date herewith to effect the oxidation in a gaseous medium containing an inhibitor.
it is an object of the present invention to provide a process for improving the surface characteristics of carbon fibers thereby to improve the adhesion between them and a matrix, particularly a matrix of plastics material.
According to the present invention carbon fibers are surface treated by immersion in an aqueous oxidizing agent.
Preferably the aqueous oxidizing agent is a hypochlorite solution containing available chlorine.
One very desirable way of obtaining the hypochlorite solution is to generate it by electrolysis of a chloride solution using the carbon fibers as one electrode.
It may also be convenient to pre-clean the carbon fibers by treatment with a conventional cleaning solvent in order to remove any gross surface contamination.
In both the pre-cleaning stage and the aqueous oxidizing stage it is very desirable to make use of ultrasonic agitation in order to ensure good contact between the relevant liquid and the fibers.
In order that the present invention may more readily be understood an embodiment of the same will now be described by way of example.
In this embodiment a 15 gm batch of carbon fibers, each approximately 7.5 microns in diameter and 33 cms. long was immersed in a bath of trichlorotrifluoroethane and ultrasonic agitation at 13 kHz was applied for 10 minutes. The fibers were then removed from the bath and dried in a cool oven to remove all traces of the solvent.
The fibers were then placed in a bath containing 5 percent by weight of sodium chloride and 0.25 percent by weight of sodium hydroxide in water. The fibers were connected to the anode and were at the same time subjected to ultrasonic agitation at 13 kHz. A copper cathode was also inserted in the bath and current was passed between the cathode and anode at a current density of 2 amps per square inch of carbon fiber surface and at a voltage of 12 volts. After treatments for 5 minutes in this bath (which generated free chlorine) the carbon fibers were removed, rinsed in water and dried.
The carbon fibers were then incorporated into an epoxide resin matrix in the proportion of 55 percent by volume and the resulting composite was tested in a 3 point bend test on a 1 inch beam. The interlaminar shear strength of the composite was 6,275 p.s.i. which compares with a strength of 2,000 to 3,000 p.s.i. for a similar laminate made from untreated fibers.
We claim: l. A method of surface treating carbon fibers comprising generating a hypochlorite solution containing available chlorine by electrolysis of an aqueous chloride solution using carbon fibers as the anode.
2. The method of claim 1 wherein prior to said electrolysis the carbon fibers used as the electrode are pre-cleaned by solvent cleaning.
Claims (1)
- 2. The method of claim 1 wherein prior to said electrolysis the carbon fibers used as the electrode are pre-cleaned by solvent cleaning.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB52568 | 1968-01-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3657082A true US3657082A (en) | 1972-04-18 |
Family
ID=9705900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US787558A Expired - Lifetime US3657082A (en) | 1968-01-03 | 1968-12-27 | Treatment of fibrous materials |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3657082A (en) |
| CH (1) | CH511768A (en) |
| DE (1) | DE1817581B2 (en) |
| FR (1) | FR1600656A (en) |
| GB (1) | GB1257022A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3859187A (en) * | 1972-09-25 | 1975-01-07 | Celanese Corp | Electrolytic process for the surface modification of high modulus carbon fibers |
| US4472541A (en) * | 1982-10-01 | 1984-09-18 | The Bendix Corporation | Secondary matrix reinforcement using carbon microfibers |
| US4637925A (en) * | 1984-06-22 | 1987-01-20 | Toray Industries, Inc. | Ultrahigh strength carbon fibers |
| US4927462A (en) * | 1988-12-23 | 1990-05-22 | Associated Universities, Inc. | Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems |
| US5017274A (en) * | 1987-02-25 | 1991-05-21 | Aquanautics Corporation | Method and systems for extracting oxygen employing electrocatalysts |
| US5271917A (en) * | 1989-09-15 | 1993-12-21 | The United States Of America As Represented By The Secretary Of The Air Force | Activation of carbon fiber surfaces by means of catalytic oxidation |
| US20090092831A1 (en) * | 2006-04-28 | 2009-04-09 | Toho Tenax Europe Gmbh | Carbon Fiber |
| CN112522729A (en) * | 2020-12-01 | 2021-03-19 | 宁波八益集团有限公司 | Hypochlorous acid production system and high-stability hypochlorous acid production method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3671411A (en) * | 1970-03-03 | 1972-06-20 | Us Air Force | Treatment of carbon or graphite fibers and yarns for use in fiber reinforced composites |
| IT1210610B (en) * | 1981-08-07 | 1989-09-14 | Sorin Biomedica Spa | PROCEDURE FOR THE ACTIVATION OF A PIROCARBONE TIP FOR CARDIAC STIMULATOR ELECTRODES |
| US4411880A (en) | 1982-05-17 | 1983-10-25 | Celanese Corporation | Process for disposing of carbon fibers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1062431A (en) * | 1911-09-25 | 1913-05-20 | Jean Billiter | Method of purifying carbon for carbon filaments. |
| US2439442A (en) * | 1943-02-06 | 1948-04-13 | Cabot Godfrey L Inc | Process of making hydrophilic carbon black |
| US2702260A (en) * | 1949-11-17 | 1955-02-15 | Massa Frank | Apparatus and method for the generation and use of sound waves in liquids for the high-speed wetting of substances immersed in the liquid |
| US3323869A (en) * | 1963-12-19 | 1967-06-06 | Dow Chemical Co | Process for producing expanded graphite |
| US3441488A (en) * | 1964-09-03 | 1969-04-29 | Atomic Energy Commission | Electrolytic desalination of saline water by a differential redox method |
-
1968
- 1968-01-03 GB GB52568A patent/GB1257022A/en not_active Expired
- 1968-12-27 US US787558A patent/US3657082A/en not_active Expired - Lifetime
- 1968-12-31 DE DE1817581A patent/DE1817581B2/en active Granted
- 1968-12-31 FR FR1600656D patent/FR1600656A/fr not_active Expired
-
1969
- 1969-01-03 CH CH2769A patent/CH511768A/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1062431A (en) * | 1911-09-25 | 1913-05-20 | Jean Billiter | Method of purifying carbon for carbon filaments. |
| US2439442A (en) * | 1943-02-06 | 1948-04-13 | Cabot Godfrey L Inc | Process of making hydrophilic carbon black |
| US2702260A (en) * | 1949-11-17 | 1955-02-15 | Massa Frank | Apparatus and method for the generation and use of sound waves in liquids for the high-speed wetting of substances immersed in the liquid |
| US3323869A (en) * | 1963-12-19 | 1967-06-06 | Dow Chemical Co | Process for producing expanded graphite |
| US3441488A (en) * | 1964-09-03 | 1969-04-29 | Atomic Energy Commission | Electrolytic desalination of saline water by a differential redox method |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3859187A (en) * | 1972-09-25 | 1975-01-07 | Celanese Corp | Electrolytic process for the surface modification of high modulus carbon fibers |
| US4472541A (en) * | 1982-10-01 | 1984-09-18 | The Bendix Corporation | Secondary matrix reinforcement using carbon microfibers |
| US4637925A (en) * | 1984-06-22 | 1987-01-20 | Toray Industries, Inc. | Ultrahigh strength carbon fibers |
| USRE33537E (en) * | 1984-06-22 | 1991-02-12 | Toray Industries, Inc. | Ultrahigh strength carbon fibers |
| US5017274A (en) * | 1987-02-25 | 1991-05-21 | Aquanautics Corporation | Method and systems for extracting oxygen employing electrocatalysts |
| US4927462A (en) * | 1988-12-23 | 1990-05-22 | Associated Universities, Inc. | Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems |
| US5271917A (en) * | 1989-09-15 | 1993-12-21 | The United States Of America As Represented By The Secretary Of The Air Force | Activation of carbon fiber surfaces by means of catalytic oxidation |
| US20090092831A1 (en) * | 2006-04-28 | 2009-04-09 | Toho Tenax Europe Gmbh | Carbon Fiber |
| US8834997B2 (en) * | 2006-04-28 | 2014-09-16 | Toho Tenax Europe Gmbh | Carbon fiber |
| CN112522729A (en) * | 2020-12-01 | 2021-03-19 | 宁波八益集团有限公司 | Hypochlorous acid production system and high-stability hypochlorous acid production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1257022A (en) | 1971-12-15 |
| DE1817581B2 (en) | 1975-10-23 |
| CH511768A (en) | 1971-08-31 |
| FR1600656A (en) | 1970-07-27 |
| DE1817581A1 (en) | 1969-10-16 |
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