EP0409512A2 - Fluorinated carbon fibres - Google Patents
Fluorinated carbon fibres Download PDFInfo
- Publication number
- EP0409512A2 EP0409512A2 EP90307721A EP90307721A EP0409512A2 EP 0409512 A2 EP0409512 A2 EP 0409512A2 EP 90307721 A EP90307721 A EP 90307721A EP 90307721 A EP90307721 A EP 90307721A EP 0409512 A2 EP0409512 A2 EP 0409512A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- fluorinated
- carbon fibers
- conductivity
- reaction
- 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.)
- Withdrawn
Links
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910014271 BrF5 Inorganic materials 0.000 claims description 11
- XHVUVQAANZKEKF-UHFFFAOYSA-N bromine pentafluoride Chemical compound FBr(F)(F)(F)F XHVUVQAANZKEKF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 description 48
- 238000003682 fluorination reaction Methods 0.000 description 11
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 10
- -1 Graphite Fluorides Chemical class 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012625 in-situ measurement Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides fluorinated carbon fibers having a conductivity at ambient temperature in the range of about 10⁻¹ to 10⁻² S/cm.
Description
- The present invention relates to carbon fibers. More particularly the present invention relates to carbon fibers having reduced conductivity.
- Carbon fibers, such as pitch based fibers (Amoco 120) are known and have many uses in industry including for the production of composite materials.
- These fibers are characterized by conductivity of 4.5 x 10³ S/cm, a Young's modulus of 120 x 10⁶ psi (820 GPa) and an interspacing value of 3.37 Å.
- According to the present invention it has now been found that it is possible by simple processing steps to substantially reduce the electrical conductivity of carbon fibers.
- The lowering of the conductivity of carbon fibers according to the present invention results in a new product having new and valuable properties and applications including carbon fibers for use in the preparation of cathodes for C/F/Li cells and in the preparation of surfaces capable of changing radar reflection characteristics.
- According to the present invention there are now provided fluorinated carbon fibers having a conductivity at ambient temperature in the range of about 10⁻¹ to 10⁻² S/cm.
- Preferably the fluorinated carbon fibers of the present invention are produced by the fluorination of carbon fibers with strong fluorinating agents at ambient temperature and in the substantial absence of additives.
- Preferred fluorinating agents are BrF₅ and 1F₇.
- Thus the present invention is preferably directed to fluorinated carbon fibers formed by the reaction of carbon fibers with IF₇ or BrF₅, e.g. fluorinated carbon fibers having a composition expressed by the formula
C1.6FBr0.05
and fluorinated carbon fibers having a composition expressed by the formula
C1.5FI0.03 - Graphite fluoride is usually prepared by direct reaction between graphite and elemental fluorine at elevated temperatures. Covalent, nonconducting C-F compounds are obtained which are formulated as (CF) n and(C₂F)n. Another sort of graphite fluoride compounds are intercalation compounds prepared by reaction of graphite and fluorine in the presence of additives such as HF, LiF, CuF₂ etc. as described e. g. T. Nakajima, I. Kameda, M. Endo and N. Watanabe, Carbon 24, 343, (1986) and I. Palchan, D. Davidov and H. Selig, J. Chem. Soc. Chem. Commun. (1983) 657. These compounds form well organized stage compounds exhibiting high conductivities ("Graphite Fluorides", Studies in Inorganic Chemistry (vol. 8), N. Watanabe, T. Nakajima and H. Touhara, Elsevier 1988).
- The enhanced conductivity, caused by charge transfer is strongly influenced by the fluorine concentration. Maximum conductivity is achieved at about stage 2 compound. At higher fluorine concentration the conductivity decreases due to formation of C-F bonds.
- Selig, et al. J. Fluor. Chem 12, 397 (1978) demonstrated that halogen fluorides, which are strong fluorinating reagents, react readily without additives such as HF or F₂ (except for IF₅) by fluorination of the graphitic lattice. The reaction of graphite with IF₇ can be described by the following reaction:
x C + y IF₇ > Cx (IF₅)F2y + (y-1) IF₅ - However said reaction scheme, which was published more than a decade ago has not been used since then and heretofore it has not been suggested that said reaction would be applicable to fluorinating carbon fibers or that fibers of substantially reduced conductivity could be produced in this manner.
- As can be seen, as recently as last year Hamwi et al., Synth. Metal 26, 89 (1988) prepared partially fluorinated graphite at room temperature by using different metallic and nonmetallic fluorides in the presence of fluorine and HF.
- As stated, according to the present invention it has now been found that it is possible to produce stable carbon fibers having a conductivity at ambient temperature in the range of about 10⁻¹ to 10⁻² S/cm by reacting the pristine fibers with halogen fluorides at ambient temperatures and without additives.
- While the invention will now be described in connection with certain preferred embodiments in the following examples so that aspects thereof may be more fully understood and appreciated, it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims. Thus, the following examples which include preferred embodiments will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of formulation procedures as well as of the principles and conceptual aspects of the invention.
- Batches of 50 mg of Amoco, pitch based fibers, P-120 were exposed to I1)200 mmHg of IF₇ and II) 400 mmHg of BrF₅, respectively. Duration time was about 5 days at room temperature. Weight uptake was about 120% which corresponds to a stoichiometry of C₁₈"IF₇" and C₁₂"BrF₅" respectively. The reacted fibers were heated for 4 hours up to 250oC in N₂ atmosphere. A weight loss of about 5-8% was observed.
- Chemical analyses of the treated fibers (after heating) gave the following results: C1.5FI0.03 and C1.6Fbr0.05. The electrical conductivity of the treated (fluorinated) fibers (after heating) at ambient conditions was in the range of about 10⁻¹ to 10⁻² S/cm.
- The fluorination reaction and fluorinated fibers were studied by the following techniques:
- 1) The weight uptake of the fibers in an IF₇ atmosphere was determined with a magnetic suspension balance Sartorius model 4201. For buoyancy weight corrections and pressure measurements a Baratron MKS gauge was used. A four-point probe connected to the reaction chamber via Teflon insulated nickel feedthroughs enabled simultaneous in-situ measurements of weight and resistance of single fibers.
- 2) X-Rays diffraction with a powder diffractometer and a Debye-Scherrer camera using CuK radiation.
- 3) Infrared spectra were recorded on a FTIR Bruker IFS 113V over the range of 400-4000 cm⁻¹ by using KBr pellets.
- 4) ESR measurements as a function of temperature and weight uptake were conducted on an E-line X-band spectrometer. We measured the ESR in-situ during exposure of fibers to BrF₅ of IF₇.
- 5) Conductivity as a function of temperature was measured with a four-point probe. Single fibers were mounted on an alumina holder by silver conducting paint. A Keithley 220 constant current source was used and voltage was measured with a Keithley 617 electrometer. Low temperatures were achieved and controlled by using an Air Products DISPLEX closed-cycle refrigerator. In order to prevent impurities effects, the pristine fibers were heat treated in chlorine atmosphere. To avoid sample heating effects we used a current of 10⁻⁷A.
- 6) Thermal stability measurements were made on a Stanton Redcroft apparatus (STA 780) in platinum crucibles in a N₂ flow.
- The P-120 fibers which had been exposed to BrF₅ or IF₇ for a few days showed weight uptakes of about 120% which correspond to stoichiometries of C₁₈"IF₇" and C₁₂"BrF₅". Exposure for longer periods did not show any change in color, weight uptake, X-ray diffraction and IR spectra suggesting saturation of fluorine content.
- Thermogravimetric measurements on the fluorinated fibers in a nitrogen atmosphere up to 250oC showed a gradual small loss of about 5-8% finally reaching a constant weight. The weight loss is probably due to removal of unreacted adsorbed halogen fluorides or volatile reduced products of the fluorination.
- Chemical analyses were carried out on fluorinated fibers which had been heated to 250oC in N₂. These gave the following results: C1.6FBr0.05 and C1.5FI0.03.
- In the case of IF₇, after completion of the reaction, the gases remaining in the reactor were transferred by fractional distillation at -23oC. We isolated IF₅ which was identified by IR measurements. When BrF₅ was condensed on the carbon fibers in a KEL-F tube the liquid turned dark indicating reduction to elemental bromine.
- In-situ weight uptake of fibers upon exposure to IF₇ shows a gradual increase in weight accompanied by decrease in pressure. The gradual weight increase and pressure decrease continued till about 90% of maximum weight uptake and was followed by a sharp drop in pressure and dramatic increase in weight. Time of reaction was sample dependent but in all cases we observed the same features; namely, a sharp decrease in pressure and a dramatic increase of weight close to the completion of the reaction.
- During the course of the reaction samples were removed from the balance at 25%, 50%, 75%, and 85% of the maximum weight uptake. They were analyzed by X-ray diffraction and by IR measurements before and after heating the samples in nitrogen.
- The IR spectra did not show the presence of C-F absorption bands. Considering the high sensitivity of FTIR and the very strong absorption bands of the C-F bonds, we assume that little or no fluorination occurred. X-ray diffractions of these samples showed only the graphitic reflections. By using a Debye Scherrer camera there were observed two weak satellites at 2 =24.2 and 28.7 degrees in addition to the normal graphitic (00 ) reflections.
- Heating these samples caused a complete weight loss and the X-ray diffraction shows the patterns of unreacted disordered fibers.
- In-situ resistance measurement, using a four-point probe, were done simultaneously with weight uptake, showing an initial drop in resistance followed by a gradual increase and subsequent drastic increase in the resistance. The minimum ratio for R/R0 is about 0.1 and maximum ratio 105.
- In-situ ESR experiments with magnetic field perpendicular to the fibers axes showed a gradual resonance broadening by factors of 2 and 1.2 upon exposure to BrF₅ and IF₇, respectively. During exposure the resonance of the pristine fibers at g=2.018 was also gradually shifted. The final g-value of both sorts of fluorinated fibers is g=2.002. Within the accuracy of the measurements, for both fluorinated fibers, the integrated intensity of the resonance remains constant. The fibers exposed to BrF₅ showed a single resonance for all concentrations and the fibers exposed to IF₇, above 50% showed the progressive appearance of a narrower resonance at the same g-value. Up to concentrations of the order of 80% the intensity of the resonance was temperature independent (Pauli-like), characteristic of mobile spins. The fully fluorinated fibers showed a Curie-like temperature dependence of the resonance intensity, characteristic of localized spins.
- X-ray diffractions of both fully fluorinated fibers showed in the range of 60<2ϑ>650 two diffractions at 2 = 150 and 42.30. These two diffractions are associated with the (00ℓ) out-of-plane reflection and the in-plane (100) basal plane reflection, respectively. The (00ℓ) reflection corresponds to a d-value of 5.8-5.9 A. This value is similar to the interlayer spacing of high temperature fluorinated graphite. The presence of the in-plane diffraction indicates that planarity was preserved. The absence of higher harmonics of in- and out-of-plane reflections and the fact that the in-plane reflection is more intense than that of the pristine fibers indicates that the system is disordered with short correlation length.
- The conductivity of both fluorinated fibers at room temperature is in the range of 10⁻¹-10⁻² S/cm. The diameter of the fibers increased from 10 to 18 upon fluorination. This conductivity is about 4-5 orders of magnitude lower than that of the pristine P-120 fibers but much higher than that of fluorinated graphite (<10⁻¹² S/cm). As was suggested by Hamwi, et al, ibid, this can be attributed to partial "ionicity" of the C-F bonds.
- Temperature dependence of the conductivity of pristine P-120 fibers (no changes were observed before or after the chlorine treatment) and the fully fluorinated fibers, suggests two thermally activated processes for conductivity. In the high temperature region (T>100K) the activated process seems to be the same for pristine and fluorinated fibers with activation energies being comparable (E=100-200K). However in the low temperature region (T<100K) the fluorinated fibers show higher activation energies (E=10K) than that of the pristine fibers (E=1K). This suggests that the fluorination process contributes to an increase of the potential barrier of the low temperature activated process without influence on the high temperature one.
- Although the functional behaviour of the resistivity versus temperature is very similar for the pristine fibers and the fluorinated fibers, the former exhibits a five order of magnitude lower resistivity. This may suggest that the concentration of the charge carriers is dramatically reduced in the fluorinated fibers. The change from Pauli to Curie-like behaviour with no significant change in the total number of spins support the assumption of reduction in the number of charge carriers due to fluorination. The fluorinated fibers were evaluated electrochemically in a Li battery by VARTA GmbH. As cathode material they showed a constant discharge of 3.1V.
- The results obtained suggest the following mechanism for the reaction between P-120 fibers upon exposure to IF₇: At the beginning of the reaction the weight uptake of IF₇ is caused by absorption in the graphite fibers (IR spectra give no evidence of fluorination in the bulk). The partially reacted samples give only the (002) and (004) diffraction peaks of the pristine fibers (together with another two weak satellites). This indicates that the halogen fluorides penetrate into the fibers probably by an absorption process and not via mechanism of intercalation. The in-situ resistance showing an initial decrease in resistance may be due to surface effects of halogen fluoride adsorption. The in-situ ESR measurements showing a constant resonance intensity and a shift of the resonance can be attributed to disorder effects caused by the halogen fluoride absorption. This is consistent with the temperature independent ESR intensity observed up to weight uptake of 85%. Since upon completion of the reaction the fibers are clearly fluorinated, it is concluded that two steps are involved. First, an absorption (probably chemisorption) of the halogen fluoride causing increasing disorder of the fibers and probably slight fluorination of the surface. The second step is fluorination of the bulk. Finally, it is important to note and emphasize that by exposure of P-120 fibers to halogen fluorides according to the present invention it is now possible to obtain stable moderately low conducting fibers.
- It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (4)
1. Fluorinated carbon fibers having a conductivity at ambient temperature in the range of about 10⁻¹ to 10⁻² S/cm.
2. Fluorinated carbon fibers according to claim 1 formed by the reaction of carbon fibers with IF₇ or BrF₅.
3. Fluorinated carbon fibers having a composition expressed by the formula
C1.6FBr0.05
C1.6FBr0.05
4. Fluorinated carbon fibers having a composition expressed by the formula
C1.5FI0.03
C1.5FI0.03
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IL90992 | 1989-07-16 | ||
| IL90992A IL90992A0 (en) | 1989-07-16 | 1989-07-16 | Carbon fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0409512A2 true EP0409512A2 (en) | 1991-01-23 |
| EP0409512A3 EP0409512A3 (en) | 1991-12-04 |
Family
ID=11060178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19900307721 Withdrawn EP0409512A3 (en) | 1989-07-16 | 1990-07-13 | Fluorinated carbon fibres |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0409512A3 (en) |
| IL (1) | IL90992A0 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5587110A (en) * | 1993-10-05 | 1996-12-24 | Daikin Industries, Ltd. | Composition being capable of imparting conductivity and non-tackifying property, paint using the composition, and roller |
| CN106592215A (en) * | 2016-12-19 | 2017-04-26 | 曲阜师范大学 | Method for preparing fluorine content- and dimension-adjustable carbon fluoride fibers |
| CN112281241A (en) * | 2020-10-27 | 2021-01-29 | 福建永荣锦江股份有限公司 | Multifunctional white fluorinated graphene/chinlon 6 fiber and preparation method thereof |
| CN117702536A (en) * | 2023-12-08 | 2024-03-15 | 湖南隆深氢能科技有限公司 | Carbon paper with excellent mechanical properties for fuel cell, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3674432A (en) * | 1969-10-20 | 1972-07-04 | R I Patents Inc | Superstoichiometric carbon monofluoride and methods for preparing stable carbon monofluorides of various stoichiometries |
| EP0015729A2 (en) * | 1979-03-02 | 1980-09-17 | Celanese Corporation | Process for the formation of intercalated carbonaceous fibrous material of increased electrical conductivity and fibrous material thus obtained |
-
1989
- 1989-07-16 IL IL90992A patent/IL90992A0/en unknown
-
1990
- 1990-07-13 EP EP19900307721 patent/EP0409512A3/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3674432A (en) * | 1969-10-20 | 1972-07-04 | R I Patents Inc | Superstoichiometric carbon monofluoride and methods for preparing stable carbon monofluorides of various stoichiometries |
| EP0015729A2 (en) * | 1979-03-02 | 1980-09-17 | Celanese Corporation | Process for the formation of intercalated carbonaceous fibrous material of increased electrical conductivity and fibrous material thus obtained |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5587110A (en) * | 1993-10-05 | 1996-12-24 | Daikin Industries, Ltd. | Composition being capable of imparting conductivity and non-tackifying property, paint using the composition, and roller |
| CN106592215A (en) * | 2016-12-19 | 2017-04-26 | 曲阜师范大学 | Method for preparing fluorine content- and dimension-adjustable carbon fluoride fibers |
| CN112281241A (en) * | 2020-10-27 | 2021-01-29 | 福建永荣锦江股份有限公司 | Multifunctional white fluorinated graphene/chinlon 6 fiber and preparation method thereof |
| CN117702536A (en) * | 2023-12-08 | 2024-03-15 | 湖南隆深氢能科技有限公司 | Carbon paper with excellent mechanical properties for fuel cell, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0409512A3 (en) | 1991-12-04 |
| IL90992A0 (en) | 1990-02-09 |
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