US3639140A - Process for carbonized cellulose fiber or the products thereof - Google Patents

Process for carbonized cellulose fiber or the products thereof Download PDF

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US3639140A
US3639140A US863518A US3639140DA US3639140A US 3639140 A US3639140 A US 3639140A US 863518 A US863518 A US 863518A US 3639140D A US3639140D A US 3639140DA US 3639140 A US3639140 A US 3639140A
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ammonium
strength
fiber
treated
cloth
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Kazuo Miyamichi
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Nitto Boseki Co Ltd
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Nitto Boseki Co Ltd
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    • 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
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Sofocleous [2]] Appl' N05 8635 Attorney-Irons, Birch, Swindler& McKie 30 Foreign Application PliOl'itY 111116 [571 ABSTRACT 061. 12, 1968 Japan ..43/74455 Cellulose fiber of the Product thereof treated with a Strength Sept. 5, 1969 Japan... increasing agent selected from the group consisting of (A) am- SEPL 5, 1969 Japan. monium sulfate, ammonium bisulfate, ammonium sulfite, am- Sept.
  • the present invention concerns a process for carbonizing cellulose fiber or the product thereof characterized by treating cellulose fiber or the product thereof with a strength increasing agent obtained by the combination of sulfur-containing acid and nitrogen-containing base or with a treating agent obtained by adding a flame resistance improving agent to said strength increasing agent, thereafter carbonizing said cellulose fiber or product thereof by the heat treatment at a temperature of up to about 1,000 C. in an inert atmosphere and further if necessary carbonizing or graphitizing the thus heat-treated fiber or product thereof by the heat treatment at a temperature of about 1,000 C. or higher in an inert atmosphere.
  • a process for producing carbon fiber or graphite filament using cellulose fiber as a starting material has been known for a long time.
  • W. R. Whitrey showed in U.S. Pat. No. 916,905 (1909) a process for graphitizing carbon fiber by the heat treatment at a temperature of 2,300 C. or higher.
  • British Pat. No. 1,025,499 (1964) employ the heating within a temperature of from 150 to 540 C. at a heating rate of to 30 C./8 to 30 hours. Thus, this process requires 3 to 50 days for elevating the temperature up to 540 C.
  • Japanese Pat. Publication No. 131 13/61 employs the heating to 400 C. at a heating rate of 10 to 50 C./hr. and thereafter the heating to 900 C. at a heating rate of 100 C./hr. or less.
  • the present invention relates to a new process which improves the above-mentioned conventional processes in the production of carbonlike fiber, carbon fiber, graphite filament or products thereoffrom cellulose fiber or products thereof.
  • the object of the present invention is to provide a new treating agent or strength-increasing agent which prevents the deterioration of cellulose due to the pyrolysis in the heating treatment of cellulose fiber or products thereof.
  • Another object of the present invention is to provide a process for highly reinforced flexible carbonlike fiber, carbon fiber, graphite filament or products thereof by treating cellulose fiber or products thereof with the above-mentioned strength-increasing agent in the heating treatment of cellulose fiber or products thereof.
  • Another object of the present invention is to provide a process for highly increasing the strength of the heat-treated fiber or the products thereof in the heat treatment at a temperature of 200 to 500 C. at which the deterioration of cellulose is particularly remarkable and in the heat treatment at further higher temperatures.
  • Another object of the present invention is to provide an industrially extremely excellent process which enables the heat treatment of high-heating velocity in the heat treatment of cellulose fiber or the products thereofv in order to attain the above-mentioned objects, the present invention, prior to the heat treatment of cellulose fiber or the products thereof, requires the treatment with a specific strength increasing agent.
  • This strength increasing agent is the later defined compound or a mixture prepared by the combination of sulfur-containing acid and nitrogen-containing base.
  • the sulfur-containing acid and nitrogen-containing base herein include the following compounds.
  • the sulfur-containing acid includes sulfuric acid (H sulfurous acid (H 80 thiosulfuric acid (Ii- 8 0 sulfamic acid (HSO NH and imidosulfonic acid ((HSOQ N H), and the nitrogen-containing base includes urea, urea derivatives, thiourea, thiourea derivatives and amines such as urea (CO(NH thiourea (CS(NH guanidine (NH:C(NH dicyandiamide (NH C:NHNHCN), dicyandiamidine (NH GNHNHCONHJ, triethylamine ((C H -,N triethanol amine ((CH CH OH H),
  • the strength increasing agent of the present invention is a compound or a mixture prepared by combining one or more compound of the above-mentioned sulfur-containing acid with one or more compounds of the above-mentioned nitrogencontaining base, and such a strength increasing agent is classified into the following three groups depending on the combinations thereof as a matter of convenience.
  • Mixtures prepared by the combination of a sulfur-containing acid, an ammonia and a nitrogen-containing base other than ammonia That is, mixtures of an ammonium salt of sulfur-containing acids mentioned in the above paragraph (1) with urea, a urea derivative, thiourea, a thiourea derivative or an amine.
  • a strength increasing agent prepared by mixing an ammonium salt in the above-mentioned paragraph (l) with urea, thiourea, guanidine, triethanolamine or the like.
  • Strength increasing agent prepared by the combination of sulfur-containing acid and nitrogencontaining base other than ammonia That is, a strength increasing agent prepared by the combination of a sulfur-containing acid with urea, 21 urea derivative, thiourea, a thiourea derivative or an amine.
  • a strength increasing agent prepared by the combination of a sulfur-containing acid with urea, 21 urea derivative, thiourea, a thiourea derivative or an amine For example, sulfuric acidguanidine, sulfuric acid-ethylenediamine, sulfuric acid-dlicyandiamine or a strength increasing agent prepared by adding urea, thiourea, aniline, triethanolamine or the like to sulfuric acid, sulfurous acid or sulfamic acid.
  • the ammonium salt of paragraph 1) may be a mixture of 2 or more members thereof, and the strength increasing agent of paragraph (2) may be prepared by adding one or more kinds of such nitrogen-containing bases as urea and the like to two or more kinds of ammonium salts. Further, the strength increasing agent of paragraph (3) may be prepared by further adding 1 or more kinds of such nitrogen-containing bases as urea and the like to such a compound as sulfuric acidguanidine, sulfuric acidethylenediarnine, etc.
  • thiosulfuric acid and imidosulfonic acid do not exist as a single compound but only in the form of the compound of said acids combined with other compound. Accordingly, the above-mentioned strength increasing agent of paragraph (3) does not include the case of thiosulfuric acid and imidosulfonic acid being the acid component thereof.
  • Ammonium thiosulfate and ammonium imidosulfonate are actually existing compounds and exhibit the excellent strength increasing effect mentioned later.
  • FIGS. are described below.
  • FIG. 1 shows the relationship between the strength of heattreated cloth obtained and the temperature of heat treatment, in the heat treatment of viscose rayon cloth wherein A represents the case of heat treatment in nitrogen and B, that in air;
  • FIG. 2 the relationship between the strength of heat-treated cloth obtained and the temperature of heat treatment, in the heat treatment of viscose rayon cloth preceedingly treated with a strength increasing agent wherein A represents the case of ammonium sulfate-diammonium hydrogen phosphate mixture system and B, the case of single ammonium sulfate system;
  • FIGS. 3 and 4 the relationship between the adhesion percentage of ammonium salt of sulfur-containing acid to viscose rayon cloth and the strength of the heat-treated cloth obtained in the heat treatment of viscose rayon cloth preceedingly treated with the said salt
  • A represents the case of ammonium sulfamate
  • B the case of ammonium sulfate
  • C the case of ammonium imidosulfonate
  • D the case of ammonium sulfite
  • E the case of ammonium thiosulfate
  • F the case of ammonium bisulfate
  • FIG. 5 the relationship between the composition of the ammonium saIt-nitrogen-containing base strength increasing agent and the obtained strength of the heat-treated cloth in the heat treatment of viscose rayon cloth precedingly treated with the said strength increasing agent
  • A represents the case of ammonium sulfite-urea system
  • B the case of ammonium sulfite-thiourea system
  • C the case of ammonium bisulfate-urea system
  • D the case of ammonium sulfitetriethanol amine system
  • FIG. 6 the relationship between the adhesion percentage of the sulfur-containing acid-nitrogen-containing base strength increasing agent and the obtained strength of heat-treated cloth in the heat treatment of the viscose rayon cloth preceedingly treated with the said strength increasing agent
  • A represents the case of sulfuric acid-urea system
  • B the case of sulfuric acid'guanidine
  • C the case of sulfuric acidthiourea system
  • D the case of sulfuric acid-triethanol amine system
  • E the case of sulfuric acid-ethylene-diamine
  • F the case of sulfuric acid-dicyandiamine
  • FIGS. 7 and 8 the relationship between the composition of the sulfur-containing acid-nitrogen-containing base strength increasing agent and the obtained strength of the heat-treated cloth in the heat treatment of viscose rayon cloth preceedingly treated with the said strength increasing agent
  • A represents the case of sulfuric acid-urea system
  • B the case of sulfuric acid-triethanolamine system
  • C the case of sulfuric acid-thiourea system
  • D the case of sulfamic acidtriethanolamine system
  • E the case of sulfamic acid-urea system
  • F the case of sulfamic acid-urea (40 percent) system
  • G the case ofsulfamic acid-thiourea system.
  • FIG. 1 is an example which shows this tendency, and shows the relationship between the obtained tensile strength of heattreated cloth and the temperature of heat treatment when viscose rayon diagonal cloth is heated up to the specified temperatures at a heating rate of 5 C./min. and heat-treated at each temperature for 1 hour respectively.
  • the heat treatment of cellulose fiber soaked in the above-mentioned strength-increasing agent includes the temperature of remarkable strength reduction at a temperature of to C., but suddenly recovers the strength at a temperature of higher than 180 C.
  • this heat treatment of such processed fiber affords flexible heat-treated fiber having high strength at a temperature of 280 C. or higher at which the heat treatment of cellulose fiber not soaked in such a strength increasing agent simply gives ex-.
  • the strength increasing action of strength increasing agent relates to the adhesion percentage or the mixing ratio of such a nitrogen-containing base urea with a sulfur-containing acid.
  • ammonium salt-nitrogen-containing base system or sulfur-containing acid-nitrogen-containing base (excluding ammonia) system is used as a strength increasing agent, it is observed that the strength of heat-treated fiber or the products thereof decreases slowly or suddenly when the adhesion percentage of the strength increasing agent exceeds a certain value.
  • the strength increasing action thereof also depends on the mixing proportion of nitrogen-containing base with ammonium salt or sulfur-containing acid which is the acid component of said ammonium salt, and it is recognized that, with respect to every strength increasing agent, the most suitable mixing ratio or the preferable mixing ratio exists.
  • the strength increasing agent of the present invention having the above-mentioned strength increasing action is subsequently described concretely.
  • FIGS. 2 to 4 show the strength increasing action of strength increasing agents obtained by the combination of sulfur-containing acid and ammonia, that is, of ammonium salts of sulfur-containing acid.
  • FIG. 2 shows the relationships between the strength of the heat-treated cloth and the temperature of dbl b d ltl heat treatment in the cases where two pieces of viscose rayon diagonal cloth are individually soaked in aqueous solutions of two strength-increasing agents such as ammonium sulfate and ammonium sulfate containing 15 weight percent of the later tion of ammonium bisulfate, dried and allowed to stand at room temperature for 1 day or more without any further processing.
  • two strength-increasing agents such as ammonium sulfate and ammonium sulfate containing 15 weight percent of the later tion of ammonium bisulfate
  • such britdescribed flame-resistance-improving agent of diammonium 5 tle action may be involved in a series of steps of soaking, dryhydrogen phosphate, the adhesion percentage of the former ing and heat treatment, resulting in the reduction of the strength increasing agent is 41.6 percent and that of the latter strength of starting material fiber or the products thereof. is 44.8 percent (which is the total adhesion ratio of ammoni- After all, the highly strong heat-treated fiber or the products um sulfate and diammonium hydrogen phosphate) and both thereof may not be obtained.
  • imidosul- ⁇ Tensile strength (kg/2.5 2.7-3.1 (1.0 8.1 12.1 12. 0 15.8 10.1 Ionate. 0111.).
  • Ammonium Adhesion percentage (per- 0 22.7 37. 6 42.5 51.7 66.3 78.15
  • ammonium bisulfate when the adhesion percentage is higher than about 10 percent, the strength of heat treated cloth decreases. Therefore, in the case of using ammonium bisulfate, the soaking treatment should be carried out so as to give about 10 percent of adhesion percentage. It is considered that such behavior of ammonium bisulfate is due to its brittle action against cellulose the action of acidic H existing in the molecule of ammonium bisulfate. For example,
  • he t-teste Cloth. is issribs Tables 2 and 3 show the results when viscose rayon diagonal cloth is treated with strength increasing agent prepared by mixing urea, thiourea or triethanol amine with ammonium sulfate, ammonium sulfamate or ammonium imidosulfonate and thereafter heattreated in air at 250 C. for 2 hours and viscose rayon cloth tnolders if it is soaked in an aqueous solu further at 300C. for 2 hours.
  • FIG. 5 shows the cases of mixing urea, thiourea or triethanolamine with ammonium sulfite and mixing urea with ammonium bisulfate.
  • FIG. 5 when viscose diagonal cloth is soaked in each aqueous solution of the above-mentioned strength increasing agents so as to produce almost constant adhesion percentage of ammonium salt and to vary the adhesion ratio of the nitrogen-containing base, wrung, dried, and thereafter heattreated in air at 250 C. for 2 hours and further at 300 C. for 1 hour, shows the relationship between the strength of heat-treated cloth and the composition of each strength increasing agent.
  • the adhesion percentages of ammonium salt to the starting material cloth, with respect to each strength-increasing agent are as follows:
  • ammonium thiosulfate as the ammonium salt, the effect of base almost identical with that of the cases of other ammonium salt can be obtained as well.
  • ammonium thiosulfate-base system is to be described in examples below.
  • the most effective base when combined with ammonium salt, is urea and thiourea.
  • Triethanolamine, guanidine and triethylamine in this case, belong to a second class as the compound exerting the base effect.
  • Dicyandiamide, dicyandiarnidine, aniline, pyridine and the like belong to the group of compounds exerting relatively low base effect.
  • FIG. 7 when viscose rayon diagonal cloth is soaked in each aqueous solution of sulfuric acid-urea system, sulfuric acid-thiourea system and sulfuric acid-triethanolamine system strength in creasing agents so that the adhesion percentages of sulfuric 4O acid, which are the acid component of the said strength increasing agents, are almost constant such as 15.0 percent, 1 L3 percent and 5.9 percent, respectively, and so that the adhesion percentages of base components thereof are varied, and thereafter heattreated in the same manner as above, shows the relationship between the mixing ratio of each strength increasing agent and the strength of heat-treated cloth.
  • FIG. 8 shows the case of sulfamic acid base system.
  • MG. 8 when viscose rayon diagonal cloth is soaked in an aqueous solution of respective strength increasing agent prepared by mixing urea, thiourca or triethanolamine with sulfamic acid at respective suitable mixing ratio and subsequently heat-treated in air at 250 for 2 hours and further at 300 C. for 1 hour, 55
  • FIGS. 6 to it show the fact that, in the case of such strength increasing agents, the strength of heattreated cloth also relates to the adhesion percentage of strength increasing agent and to the composition thereof, as in the case of the aforesaid single ammonium salt system or ammonium salt-nitrogen-containing base system.
  • H6. 6 shows that the strength of heat-treated cloth increases in harmony with the increase of adhesion percentage of strength increasing agent and that, when the adhesion percentage exceeds a certain value, the strength gradually or suddenly decreases. ln the case of sulfamic acid-urea system, FIG. ti shows that, within a certain mixing range, sulfamic acid with 40 percent adhesion percentage exerts stronger strength increasing action than that with 20 percent aehesion percentage.
  • FIGS. "7 and 8 show that, with respect to every strength increasing agent, the most suitable or preferably mixing ratio exists.
  • the strength increasing agent of sulfurous acid-base system behaves in the same way as that of sulfuric acid-base system and exerts almost identical strength increasing action. This is described in examples below.
  • the strength increasing agents described in detail above exert strength increasing action even if the heating atmosphere is changed from air to an inert. atmosphere. Further,
  • Table 4 is an example which shows this fact, and shows the results when viscose rayon diagonal cloth is treated with an aqueous solution of treating agent of ammonium imidosulfonate and urea with a weight ratio of 2:1 so as to make the adhesion percentage thereof4i.l percent and thereafter heattreated in air and in nitrogen which is an inert atmosphere.
  • the case where the nontreated viscose rayon diagonal cloth is heattreated under the identical conditions is ,9 sho nrtlivn rtli inert-rising agent of respective mixing ratio to the "table 4 shows the fact that, in this case, even i! the at- .slartlup umtrriul diagonal cloth is controlled so in: to main: the mosphcre of heat treatment is air or nitrogen, almost similar ill.
  • inert gas helium, argon, carbon dioxide or the like may be used, in addition to nitrogen.
  • the present inventors by heat-treating cellulose fiber or the products thereof, precedingly treated with a kind of strength increasing agents, in air within a temperature range of 200 to 350 C. and then further heattreating the thus heat-treated fiber or the products thereof in an inert atmosphere at a temperature of up to about 1,000 C., have succeeded in the production of stronger carbonlike fiber or the products thereof than the heat-treated substances under the same conditions of nontreated cellulose fiber.
  • This process requires the heat-treatment for a long period of time, for example, 2 hours at 250 C. andfurther l to lioggs at 300 C., in order to avoid the rapid oxidative combustion in the heat treatment at a temperature of 200 to 350 C.
  • a process employing the heat treatment in an inert atmosphere after the heat treatment in air as in the above-mentioned manner requires two types of furnaces or two steps of heat treatment, and is not an industrial satisfactory process although this process affords highly strong carbonlike fiber or the products thereof and highly efficiently produces the same as compared with the conventional technique for the production of carbonlike fiber.
  • the process for carbonizing cellulose fiber or the products thereof of the present invention wherein cellulose fiber or the products thereof are treated with a kind of the above-mentioned strength increasing agents, thereafter the thus treated fiber or the products thereof are converted to carbonlike substances by the heat treatment at a temperature of up to about l,000 C. in an inert atmosphere and if necessary, the thus heat-treated fiber or the products thereof are carbonized or graphitized by the further heat treatment at a temperature of higher than about 1,000 C. in an inert atmosphere, as is clear from examples shown below, enables the production of highly strong carbonlikc fiber, and further excellent carbon fiber, graphite fiber or the products thereof by the heat treatment with such a high heating rate as l to 5 C./1nin. over the temperature range offrom room temperature to l,000 C., and does not require two types of'furnaces or two steps of heat treatment.
  • this process is an industrially extremely advantageous process.
  • the heating rate of the said treated substance is not necessarily limited within the above-mentioned heating rate.
  • this invention includes the case of heat treatment at a heating rate of less than l C./min.
  • Carbon fiber or graphite fiber with a carbon content of about 95 percent or above can be produced by heattreating the carbonlikc fiber prepared according to the above-mew tioned process of the present invention (carbon content: up to about 90 percent) at a temperature of higher than about l,()00 C. according to the conventional process. Even in this case, however, if the highly strong carbonlike fiber produced by the process of the present invention is used as the starting material, the stronger carbon fiber or graphite fiber than the conventional carbon or graphite fiber can evidently be ob tained.
  • air incorporated in the heat treatment furnace air initially contained in the cloth or oxygen contained in an inert gas may cause the deterioration of heattreated fiber or the products thereof due to the oxidation by said air or oxygen.
  • Such a heat treatment may often afford the lower strength to the heat-treated fiber or the products thereof than the experimental heat treatment where the heat treatment atmosphere is completely replaced by an inert gas, in order to avoid this disadvantage, the starting material fiber or the products thereof may be soak-treated with a strength increasing agent, to which is precedingly added such a compound as ammonium phosphates, guanidine phosphate, aluminum ammonium sulfate, tetrakis hydroxymethyl phosphonium chloride (THPC) and the like, which is called as a flameresistance-improving agent clarified in the present inventors invention relating to the process for the production of flameresistant fiber.
  • a strength increasing agent such a compound as ammonium phosphates, guanidine phosphate, aluminum ammonium sulfate, tetrakis hydroxymethyl phosphonium chloride (THPC) and the like, which is called as a flameresistance-improving agent clarified in the present inventors invention relating to the process
  • the soak treatment of the starting material cellulose fiber or the products thereof with an aqueous solution of the above-mentioned compound called as a flame-resistance-improving agent affords the heat-treated fiber or the products thereof which do not involve not only the combustion but also the ember combustion and the reduction to ashes, in other words, the heat-treated fiber or the products thereof excellent in oxidation resistance.
  • the present invention is applied after treating cellulose fiber or the products thereof with a treating agent prepared by adding the above-mentioned flame-resistance-improving agent to a strength increasing agent of the present invention having been described in detail, even if oxygen is contained in an inert atmosphere, the heat-treated fiber or the products thereof excellent in oxidation resistance due to the presence of flame-resistance-improving agent can be produced, and thereby the oxidative deterioration due to said oxygen or air contained in the starting material fiber or the products thereof may be inhibited so as to give preferable results.
  • Table 5 shows the results of the cases where diammonium hydrogen phosphate, triammonium phosphate, guanidine phosphate, THPC and aluminum ammonium sulfate are employed as a flame-resistance-improving agent.
  • the case of ammonium dihydrogen phosphate also exerts the identical action.
  • two kinds or more of flame resistance improving agents may simultaneously be used, and the amount of addition thereof may be small as compared with that of strength increasing agent.
  • NorE.-Startin material cloth viscose rayon diagonal cloth conditions of heat trcatmonti 250 C. l hour plus 300 C. 2 hours (in air):
  • A not burning into i]. flame; no umber combustion; no reduction to ashes.
  • the condition of heat treatment of the present invention should suitably be determined depending on the texture, shape, etc., of the starting material fiber or the products thereof. For example, when a big rattan, thick woven stuff, thick nonwoven cloth or felting is heattreated, heat generated by the pyrolysis thereof is liable to be stored up inside the texture thereof, and thereby the abnormal heat generation is involved so that the temperature controlling may sometimes become difficult. In this case, such a method as reducing the heating rate should be applied.
  • the properties concerning the strength of heat-treated fiber or the products thereof obtained by the present invention depend on the kind of strength increasing agents, the adhesion percentage thereof, mixing ratio thereof, heat treatment conditions and so on, and in addition thereto, relates to the microstructure of starting material cellulose. That is, generally, the higher the degree of orientation ofstarting material cellulose, the larger the strength of the heattreated fiber or the products thereof and the smaller the elongation thereof.
  • the heat-treated fiber of such a highly crystal-- line cellulose fiber as polynosic fiber, cotton or the like is generally brittle, but such brittleness can be avoided if such crystalline starting material fiber is precedingly treated according to such a known method as mercerization or the like to reduce the degree of crystallization thereof and then heattreated.
  • the starting material fiber or the products thereof are not limited within the fiber or the products thereof singly comprising cellulose fiber, but include the fiber or the products thereof which is prepared by mixing such a known fiber able to be carbonated by pyrolysis as polyacrylonitrile fiber, polyvinylalcohol fiber or the like with cellulose fiber.
  • cellulose fiber includes not only the fiber singly comprising cellulose fiber but also all of the fibers composed of the every above-mentioned materials, and represents every kind of the above-mentioned fibers.
  • the present invention in the production of carbonlike fiber, carbon fiber, graphite fiber or the products thereof from cellulose fiber, enables the preparation of carbonlike fiber or the products thereof having the strength several times higher than the case ofusing nontreated cellulose fiber as a starting material even at a temperature of 200 to 500 C. which belongs to the most dangerous temperature range wherein the mechanical properties of the carbonated fiber may be deteriorated, by precedingly treating cellulose fiber or the products thereof with a strength increasing agent provided for in the present invention or a treating agent prepared by adding a flame resistance improving agent to said strength increasing agent, and subsequently by heattreating the thus treated fiber or the products thereof at a temperature of up to about 1,000 C. in an inert atmosphere, and thereby, enables the highly efficient production of carbon fiber, graphite fiber or the products thereof having the further higher strength than that of the conventional art, by the heat treatment of carbonation or graphitization at further higher temperature.
  • EXAMPLE 1 By soaking viscose method cellulose fiber (5.5 d; tensile strength (dry): 10.7 g.; tensile tenacity (dry): 1.9 g./d; elongation: 21.3 percent) in an aqueous solution of ammonium sulfate with a concentration of 400 g./l., wringing the thus soaked fiber with a wringing percentage of 100 percent and drying the wrung fiber at [20 C. for l5 minutes, cellulose fiber having the adhesion percentage of ammonium sulfate of 40 percent was prepared. Thereafter, said cellulose fiber and nontreated cellulose fiber were individually placed in a respective sealed container replaced by nitrogen and heattrcated by elevating the temperature, at a heating rate of 5 C/min. to 400 and 600 C. respectively.
  • A represents the heat-treated fiber obtained by directly heating the treated cellulose fiber in nitrogen
  • B represents the heat-treated fiber obtained by heattreating the nontreated cellulose fiber in the same manner as A
  • C represents the heat-treated fiber obtained by heating the treated cellulose fiber in air and thereafter in nitrogen. That is, A is prepared by the process of the present invention; B, by the conventional method; and C, by other process of the present inventors in- Men o -,7
  • EXAMPLE 2 Two pieces of diagonal cloth comprising viscose rayon l .5 d.) spun yarn (thread density: longitudinal, 36 threads/2.5 cm. of width, transverse, 36 threads/2.5 cm. of width; weight: 280 g./m. were respectively soaked in (A) an aqueous solution of ammonium sulfate (concentration: 400 g./l.) and in (B) a mixed aqueous solution of ammonium sulfate (concentration: 400 g./l.) and diammonium hydrogen phosphate (concentration: 70 g./l.), the thus soaked two pieces of diagonal cloth were wrung at a wringing percentage of 100 percent and subsequently dried at C.
  • A an aqueous solution of ammonium sulfate
  • B a mixed aqueous solution of ammonium sulfate
  • diammonium hydrogen phosphate concentration: 70 g./l.
  • rayon (denier o1 d) spun yarn (thread density: longitudinal, of width, transverse, 36 threads/2.5 cm. of
  • treating agent comprising 1,000 g. of ammonium sulfate. 500 g. of urea. 75 g. of
  • the heat-treated cloth at 500 C. Weight loss: 48.5 percent; Tensile strength: 8.62 kg./2.5 cm. of width The heabtreated cloth at l,000 C.
  • EXAMlfLE s The same starting material diagonal cloth as in example 3 wassoaked in an aqueous solution of treating agent comprising 410 g. of sulfurous acid (net weight in sulfurous acid water), 750 g. of urea, g. of diammonium hydrogen phosphate and 2,000 cc. of water, wrung by mangle and then EXAMPLE 6 A bundle of viscose rayon fiber (denier of monofilament: 5.5 d; tensile strength: 1.9 g./d; elongation: 21.3 percent) is soaked in an aqueous solution of ammonium sulfate (400 g/l.
  • this bundle oftreuted fibers was heattreated in nitrogen by elevating the temperature at a rate of 1 C./min. over a range of from room temperature to 220 C., at a rate of 3 C./min. over a range of from 220 to 600 C. and at a rate of5 CJminfover a range of from 600 to 1,000 C. so as to obtain abundle of carbonlike fibers having a tensile strength of 3.3 g./d, elongation of 1.7 percent and carbon content of 90.3 percent.
  • this bundle of carbonlike fibers was suspended perpendicularly in a graphite tube-shaped heatingbody (Tamnan furnace) having internal diameter of 2 cm. and heating portion length of 40 cm., a weight was suspended at the lower terminal of said bundle as a load of6.0 mg./d and the air in said heating body was replaced by argon. Thereafter, said treated bundle of fibers was heated in order to elevate the temperature from l,000 to 2,800C. in about 2 hours and further heattreated at 2,800 C. for l5 minutes.
  • a bundle of the same starting material fibers as in example 6 was soaked in an aqueous solution of treating agent comprising 490 g. of sulfuric acid, 600 g. of urea and 2,500 cc. of water, thereafter wrung and dried so as to obtain a bundle of treated fibers with the adhesion percentage of solid component being 57.0 percent. Subsequently, this bundle of fibers was heated in nitrogen up to l,000 C. and hcattreated in the same manner as in example 6 so as to obtain a bundle of carbonlike fibers with carbon content of 9 l .3 percent. Thereafter, this bundle of carbonlike fiber was suspended in the same graphite heating body as that of example 6, heated in argon from L000 to 2,800 C.
  • treating agent comprising 490 g. of sulfuric acid, 600 g. of urea and 2,500 cc. of water, thereafter wrung and dried so as to obtain a bundle of treated fibers with the adhesion percentage of solid component being 57.0 percent.
  • the obtained heat-treated fiber was graphitelike fiber having a tensile strength of 3.61 g./d, elongation of 0.45 percent, Young's modulus of 18,100 kgjmm. and carbon content of 99.9 percent.
  • a process for carbonizing cellulose fiber or the products thereof which comprises the steps of:
  • ammonium imidosulfonate and mixtures thereof;
  • B a mixture ofat least one compound selected from the group consisting of ammonium sulfate, ammonium blsulfate, ammonium sulfite, ammonium bisulfite, ammonium thiosulfate, ammonium sulfamate, and ammonium imidosulfonate with at least one organic nitrogen base, and
  • C a mixture of an organic nitrogen base and an acid selected from the group consisting of sulfuric acid, sulfurous acid and sulfamic acid;
  • step (b) heattreating the product of step (a) in an inert atmosphere at a temperature of at least about 400 C. for a period of time sufficient to bring about carbonization.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US863518A 1968-10-12 1969-10-03 Process for carbonized cellulose fiber or the products thereof Expired - Lifetime US3639140A (en)

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US4020145A (en) * 1973-01-18 1977-04-26 Celanese Corporation Carbon fiber production
US4067210A (en) * 1975-10-14 1978-01-10 The United States Of America As Represented By The Secretary Of The Army Warp knit fabric containing weft of protective yarn-covered activated-carbon yarn
US4251589A (en) * 1979-09-05 1981-02-17 Charles Romaniec Production of a substantially inert flexible textile material
US4264320A (en) * 1978-06-07 1981-04-28 Fireproof Products Limited Production of black flame-resistant flexible textile materials
US4723959A (en) * 1984-11-07 1988-02-09 Nitto Boseki Co., Ltd. Non-inflammable fiber materials and process for producing the same
US4938942A (en) * 1985-07-17 1990-07-03 International Fuel Cells Carbon graphite component for an electrochemical cell and method for making the component
US5521008A (en) * 1993-11-25 1996-05-28 Electrophor, Inc. Manufacture of activated carbon fiber
US20050262620A1 (en) * 2004-05-26 2005-12-01 Shulong Li Protective garment system having activated carbon composite with improved adsorbency
US20050266750A1 (en) * 2004-05-26 2005-12-01 Shulong Li Treated activated carbon and process for making same
CN107416820A (zh) * 2017-07-18 2017-12-01 广西大学 一种n，o，s掺杂的网状石墨化碳纳米材料的制备方法

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GB2612290A (en) * 2021-09-01 2023-05-03 Grown Graphene Ltd Graphene-like material

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US3297405A (en) * 1963-11-21 1967-01-10 Siemens Planiawerke Ag Method of carbonizing animal fiber materials
US3305315A (en) * 1962-09-20 1967-02-21 Union Carbide Corp Process for manufacturing flexible carbonaceous textile material
US3333926A (en) * 1963-10-30 1967-08-01 Union Carbide Corp Process for carbonizing cellulosic textile materials
US3441378A (en) * 1966-05-10 1969-04-29 Union Carbide Corp Process for the manufacture of carbon textiles
US3461082A (en) * 1964-10-10 1969-08-12 Nippon Kayaku Kk Method for producing carbonized lignin fiber
US3479151A (en) * 1966-01-03 1969-11-18 Hitco Method of carbonizing fibrous cellulosic materials
US3479150A (en) * 1965-07-14 1969-11-18 Hitco Carbonization method for cellulosic fibers
US3527564A (en) * 1968-04-15 1970-09-08 Stevens & Co Inc J P Process for carbonizing fibrous materials
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US3305315A (en) * 1962-09-20 1967-02-21 Union Carbide Corp Process for manufacturing flexible carbonaceous textile material
US3333926A (en) * 1963-10-30 1967-08-01 Union Carbide Corp Process for carbonizing cellulosic textile materials
US3297405A (en) * 1963-11-21 1967-01-10 Siemens Planiawerke Ag Method of carbonizing animal fiber materials
US3461082A (en) * 1964-10-10 1969-08-12 Nippon Kayaku Kk Method for producing carbonized lignin fiber
US3479150A (en) * 1965-07-14 1969-11-18 Hitco Carbonization method for cellulosic fibers
US3532466A (en) * 1965-11-16 1970-10-06 Nat Res Dev Production of carbon fibres
US3479151A (en) * 1966-01-03 1969-11-18 Hitco Method of carbonizing fibrous cellulosic materials
US3441378A (en) * 1966-05-10 1969-04-29 Union Carbide Corp Process for the manufacture of carbon textiles
US3527564A (en) * 1968-04-15 1970-09-08 Stevens & Co Inc J P Process for carbonizing fibrous materials

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020145A (en) * 1973-01-18 1977-04-26 Celanese Corporation Carbon fiber production
US4067210A (en) * 1975-10-14 1978-01-10 The United States Of America As Represented By The Secretary Of The Army Warp knit fabric containing weft of protective yarn-covered activated-carbon yarn
US4264320A (en) * 1978-06-07 1981-04-28 Fireproof Products Limited Production of black flame-resistant flexible textile materials
US4251589A (en) * 1979-09-05 1981-02-17 Charles Romaniec Production of a substantially inert flexible textile material
US4723959A (en) * 1984-11-07 1988-02-09 Nitto Boseki Co., Ltd. Non-inflammable fiber materials and process for producing the same
US4938942A (en) * 1985-07-17 1990-07-03 International Fuel Cells Carbon graphite component for an electrochemical cell and method for making the component
US5521008A (en) * 1993-11-25 1996-05-28 Electrophor, Inc. Manufacture of activated carbon fiber
US20050262620A1 (en) * 2004-05-26 2005-12-01 Shulong Li Protective garment system having activated carbon composite with improved adsorbency
US20050266750A1 (en) * 2004-05-26 2005-12-01 Shulong Li Treated activated carbon and process for making same
US20070202259A1 (en) * 2004-05-26 2007-08-30 Shulong Li Process for making treated activated carbon
US7589034B2 (en) 2004-05-26 2009-09-15 Milliken & Company Treated activated carbon and process for making same
US20110016618A1 (en) * 2004-05-26 2011-01-27 Shulong Li Protective garment system having activated carbon composite with improved absorbency
CN107416820A (zh) * 2017-07-18 2017-12-01 广西大学 一种n，o，s掺杂的网状石墨化碳纳米材料的制备方法
CN107416820B (zh) * 2017-07-18 2020-07-31 广西大学 一种n，o，s掺杂的网状石墨化碳纳米材料的制备方法

Also Published As

Publication number Publication date
DE1951020C3 (de) 1974-04-25
DE1951020B2 (de) 1973-08-30
DE1951020A1 (de) 1970-08-13
GB1284415A (en) 1972-08-09

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