EP0068751B1 - Boronated mesophase pitch derived carbon fibres - Google Patents
Boronated mesophase pitch derived carbon fibres Download PDFInfo
- Publication number
- EP0068751B1 EP0068751B1 EP82303176A EP82303176A EP0068751B1 EP 0068751 B1 EP0068751 B1 EP 0068751B1 EP 82303176 A EP82303176 A EP 82303176A EP 82303176 A EP82303176 A EP 82303176A EP 0068751 B1 EP0068751 B1 EP 0068751B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibre
- mesophase pitch
- pitch derived
- derived carbon
- boron
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 31
- 239000011302 mesophase pitch Substances 0.000 title claims description 30
- 229910052799 carbon Inorganic materials 0.000 title claims description 29
- 239000000835 fiber Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920001187 thermosetting polymer Polymers 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 150000001639 boron compounds Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011295 pitch Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010926 purge 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
-
- 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
- D01F11/124—Boron, borides, boron nitrides
Definitions
- the invention relates to boronated mesophase pitch derived carbon fibres and to a method for producing mesophase pitch derived carbon fibres.
- thermoset the pitch fibre by heating it in air
- carbonize the thermoset pitch fibre by heating the thermoset pitch fibre in an inert gaseous environment to an elevated temperature.
- mesophase pitch in carrying out this process rather than isotropic pitch because the carbon fibre obtained using mesophase pitch exhibits excellent mechanical properties.
- the present invention is directed to mesophase pitch derived carbon fibres which have diameters less than 30 micrometers.
- the process of the present invention overcomes the problems of the prior art and enables the carbonizing temperature to be considerably lower for producing a mesophase pitch derived carbon fibre having a relatively high Young's modulus. Furthermore, the carbon fibre produced by the present invention possesses a higher compressive strength as compared to the prior art mesophase pitch derived carbon fibres having comparable Young's moduli.
- a mesophase pitch derived carbon fibre having a diameter of less than 30 micrometers and characterised by having at least 0.1% by weight boron diffused in the lattice of the fibre.
- the invention includes a method for producing such a mesophase pitch derived carbon fibre, characterized by contacting a mesophase pitch derived fibre having a diameter of less than 30 micrometres with a boron compound, such that the fibre contains at least 0.1% by weight boron diffused in the lattice of the fibre and thereafter subjecting the fibre to heat treatment at a maximum temperature of 2000°C to 2500°C to form the carbon fibre.
- the steps of contacting and heat treating can be simultaneous or in tandem in time.
- the mesophase pitch derived fibre of the invention preferably has 0.6% by weight boron diffused in the lattice of the fibre.
- a solution such as a boric acid solution with a concentration of about 2% by weight should be used.
- thermoset mesophase pitch derived fibre which has been carbonized to 1300°C is wound on a mandrel and immersed in a 2% by weight boric acid aqueous solution for at least 24 hours, dried at a temperature of about 300°C for 17 hours, and thereafter subjected to a heat treatment at a temperature of about 2000°C in an inert atmosphere such as an argon atmosphere.
- a "yarn" or bundle of filaments is used rather than a single fibre.
- a commercial yarn typically has about 2000 filaments.
- thermoset mesophase pitch derived yarn can be boronated. This yarn must be handled more carefully than the carbonized yarn due to the relatively weak mechanical properties.
- U.S. Patent No. 3,723,605 to Ram is directed to a process of using a boron compound to reduce the temperature for graphitizing an amorphous carbon.
- the patent is directed to carbon fibres derived from organic polymeric fibrous materials such as, for example, acrylic polymer, a cellulosic polymer, a polyamide, a polybenzimidazole or polyvinyl alcohol.
- U.K. Patent No. 1,295,289 is concerned with a process for the production of a graphitized polymeric fibre which comprises pretreating a carbonized or stabilized polymeric fibre with elemental boron or a boron compound to reduce the graphitization temperature.
- the fibres used in the process of this patent however are synthetic polymeric fibres. In other words both the U.S. Patent and the U.K. Patent teach away from mesophase pitch derived fibres.
- a mesophase pitch derived yarn having 2,000 filaments was used.
- the yarn was thermoset and carbonized to 1300°C.
- Each filament has a diameter of about 10 micrometres.
- a mandrel or spool made of graphite and having a diameter of about 7cm and a height of about 12.7 cm was wrapped with a layer of carbon felt having a thickness of 0.64 cm and approximately 42.7 cm of the mesophase pitch derived yarn was wrapped on this layer.
- the yarn made about four layers.
- a second layer of carbon felt was wrapped around the layers of the yarn to define a mandrel assembly.
- the mandrel assembly was then immersed in a 2% by weight aqueous solution of boric acid for at least 24 hours and then dried at a temperature of about 300°C for about 17 hours. Immediately after drying, the mandrel assembly was charged in a graphite susceptor and placed in an induction vacuum furnace. The furnace was evacuated to 10- 5 Torr (1.33x10- 3 Pa) prior to purging the system with argon and an argon atmosphere was maintained throughout the heating cycle.
- yarns were heat treated at 2050°C, 2300°C, and 2500°C for 0, 15 and 30 minutes in each case.
- the O minute hold procedure consisted of reaching the designated peak temperature and then turning the furnace power off.
- the heating rate was such that the time required to reach 2050°C was about ten minutes while the time to reach 2500°C was about fifteen minutes.
- Table 1 shows the Young's modulus for each boronated mesophase pitch derived carbon fibre according to the present invention and control mesophase pitch derived carbon fibres which were carried through the same heat treatment but were not boronated.
- the boronated carbon fibres had a higher Young's modulus and the improvement in the boronated fibres was particularly evident for the heat treatment of 2050°C.
- the Young's modulus was measured using yarn specimens.
- the yarn was embedded in an epoxy resin and loaded at the rate of 1.27 cm per minute and the modulus was obtained using an extensometer.
- the compressive strength of the boronated carbon fibres was greater than the prior art carbon fibres.
- thermoset pitch yarn contacted with a boron solution prior to a heat treatment such as carried out in accordance with the invention.
- thermoset pitch yarn should be carbonized to about 1300°C and then contacted with a boron solution and carbonized according to the invention.
- thermoset fibre yarn is used in connection with the mandrel, then a subsequent heat treatment while the thermoset fibre remains on the mandrel results in a deterioration of mechanical properties. It is belived that this deterioration arises from the oxygen released from the thermoset fibres being maintained in the vicinity of the fibres by the carbon felt which surrounds the fibres on the mandrel.
- the boron which enters the lattice of the carbon fibres amounts to up to about 1.2% by weight. At least 0.1 % by weight boron is needed in the lattice in order to produce an appreciable improvement.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27616581A | 1981-06-22 | 1981-06-22 | |
| US276165 | 1981-06-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0068751A1 EP0068751A1 (en) | 1983-01-05 |
| EP0068751B1 true EP0068751B1 (en) | 1985-09-04 |
Family
ID=23055461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82303176A Expired EP0068751B1 (en) | 1981-06-22 | 1982-06-18 | Boronated mesophase pitch derived carbon fibres |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0068751B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS588126A (enrdf_load_stackoverflow) |
| DE (1) | DE3266025D1 (enrdf_load_stackoverflow) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723605A (en) * | 1970-06-10 | 1973-03-27 | Celanese Corp | Process for the production of a continuous length of graphitic fibrous material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1267201A (enrdf_load_stackoverflow) * | 1968-10-03 | 1972-03-15 | ||
| GB1295289A (enrdf_load_stackoverflow) * | 1968-12-09 | 1972-11-08 | ||
| JPS497527A (enrdf_load_stackoverflow) * | 1972-05-30 | 1974-01-23 | ||
| FR2424240A1 (fr) * | 1978-04-25 | 1979-11-23 | Stackpole Carbon Co | Procede pour fabriquer une feuille de graphite flexible a haute resistance |
-
1982
- 1982-06-18 JP JP10405382A patent/JPS588126A/ja active Granted
- 1982-06-18 EP EP82303176A patent/EP0068751B1/en not_active Expired
- 1982-06-18 DE DE8282303176T patent/DE3266025D1/de not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723605A (en) * | 1970-06-10 | 1973-03-27 | Celanese Corp | Process for the production of a continuous length of graphitic fibrous material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6352135B2 (enrdf_load_stackoverflow) | 1988-10-18 |
| EP0068751A1 (en) | 1983-01-05 |
| JPS588126A (ja) | 1983-01-18 |
| DE3266025D1 (en) | 1985-10-10 |
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|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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| AK | Designated contracting states |
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| 17P | Request for examination filed |
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| 26N | No opposition filed | ||
| ITPR | It: changes in ownership of a european patent |
Owner name: CESSIONE;AMOCO CORPORATION |
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