Carbon Letters Vol. 10, No. 1 March 2009 pp. 43-51 Carbon Fibers(III): Recent Technical and Patent Trends Min-Kang Seo 1, Sang-Hee Park 2, Shin Jae Kang 2 and Soo-Jin Park 1, 1 Dept. of Chemistry, Inha University, 253, Nam-gu, Incheon 402-751, Korea 2 Jeonju Institute of Machinery and Carbon Composites, 750-1, Deokjin-gu, Jeonju 561-844, Korea e-maila sjpark@inha.ac.kr (Received February 12, 2009; Accepted march 11, 2009) Abstract Carbon fibers are a new breed of high-strength materials. The existence of carbon fiber came into being in 1879 when Edison took out a patent for the manufacture of carbon filaments suitable for use in electric lamps. However, it was in the early 1960s when successful commercial production was started, as the requirements of the aerospace industry for better and lightweight materials became of paramount importance. In recent decades, carbon fibers have found wide applications in commercial and civilian aircraft, along with recreational, industrial, and transportation markets as the price of carbon fiber has come down and technologies have matured. The market for carbon fiber has experienced a good growth in recent years. The growth rate for the last 23years was about 12%. The article reviewed 9,641 Korea, U.S., Japan, Europe patents issued in the carbon fibers in order to offer additional insight for researchers and companies seeking to navigate carbon fiber patent landscape. This article will provide you with all the valuable information and tools you will need to investigate your study successfully within the carbon fiber field. This article also will save you hundreds of hours of your own personal research time and will significantly benefit you in expanding your business in the carbon fiber market. Keywords : Carbon fibers, Patent, Research, Business, Market 1. ˆ o ˆ o p v opp 90% p p p lv oqp ˆ q k (Polyacrylonitrile, p PAN), o Ë ˆ ˆ q p (Pitch, kdž ) pmp rs o ˆp o r ~ v (Precursor, ˆ eˆ rp v)p o l l l llv o p, r ~p s l PAN m [1-5]. ˆ op vp o l p ˆ q p s, s v o ˆp p q, l, r k r, r lr, rlž} l kr, r,, X Œ, rqž, ~, ol p n vp v pp, (activation) s l n n l [6-10]. ˆ o rs p, ˆ o p q pqˆ p q p l r p te v q n op, pqˆ p 300 GPa p p o Typep ˆ (HM, ˆ o 99% p ) ˆ o, pq 4.0 GPa p p o Typep (HT, ˆ o 92% p ) ˆ o, p l} m p rs l v [11-20]., PAN ˆ o, ˆ p n l p ~ p ~ q Ënt, d n l n l m. 1980 p p p 1 sq rn o e ˆ op p ˆ o rs l n~ p l p qp eq l. 1983 1985 l ~ Table 1l ˆ m p, Torayca T800H, Magnamite IM-6, IM-7, Besfight IM-500 p tˆ ˆ o ež p CFRPn r 2 ˆ op n p. 1986 l PAN n p 2 p 7GPa, r e 2.4% s p pl 2.0% }pp l p ˆ op Torayca T1000p p l e l. pp e p e p l t l. ˆ o q l k l, e d Ë r n p l Ënt p r kl n l m. q ˆ op p p l qp ~ q n l p. l v l p k }l d l rv q l n nvpp p, p }l d q p l l PAN ˆ o n eq m. rp r pp p o ~r p el ˆ o
44 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) 43-51 Table 1. rsl~ PAN ˆ o rsl~ Grade (GPa) Toray Toho Tenax Mitsubishi Rayon Heracules Torayca Besfight Pyrofil Magnamite T800H T1000H T1000 IM-400 IM-500 IM-600 MR-40 MR-50 MR-60K IM-6 IM-7 IM-8 IM-9 n e pp, e rp ~r Žp ~ q k l r or ožp, l v p p p o ~ pnp o., p v ˆ o ~p ~ q l n l eqp p r [21-27]. ˆ op n e v eˆ o p p lv p. Š Ë l kl n p lv nl krp rp m. v q p n ˆ o r p p l p l n p, pn k d n kl t p l m pn kp k o p n rp p lrk p. l ˆ om r tep (Patent Mapping)p q s l ˆ ol 1974 2007 v v 30l p p pm p, op p p no p tn p k p ~ rp p f e pn l p p p ˆ op p Žk q m. 2. Š m l 5.59 6.35 7.06 4.51 5.10 5.79 5.00 5.49 6.17 5.10 5.30 5.30 6.34 ˆ (GPa) 295 300 285 275 275 303 289 e (%) 1.9 2.1 2.4 1.5 1.7 2.0 1.7 1.9 2.1 1.7 1.8 1.6 2.2 1.81 1.80 1.82 1.74 1.76 1.80 1.77 1.80 1.82 1.77 1.77 1.80 1.79 ˆ ol r p r l o l r r p pd tp l,, p, o p p mp, qp p l opp tp m [28]. l e ˆo p ˆ om pm, ˆ o rs ˆ o p n l p ee mp, n rp l Fig. 1. o ( n). rp p rp s l p r bottom-up ep v m. p e p ˆo n el e, p ˆo v rp l l ep q p f e pn l ˆ kp p r m., p p m e o l p lr l t pp, rl l r kl o p rp ˆ v kk, kl p r p lvv kpp p p k p l l k e. p p s ˆ o r p 10,000l plp, r p o l t pv( ˆo p lp p n lv ) r ˆ o p l tl r v kp p f sr p p 9000l p l krp p r rp np p r p l p v m. r p ol, op l, rop v p p l mp, r p p p Žk m. 3. Š }k 3.1.1. r~ (1) o ˆ op o p Fig. 1l k p p p p 1981 q v o ˆ o
Carbon Fibers (III): Recent Technical and Patent Trends 45 Fig. 2. ol o ( n). Fig. 4. ol o ( ). Fig. 3. op o ( n). p r~ p 9,641 p 79%(7,680 ) v p, pl, o, p 10%(986 ), 7%(636 ), 4%(339 ) v p. p p ˆ ol p l p p o k ppp lt p. (2) o l o Fig. 2 p,, o l o ˆ o o l Š, 1981 290 p eqp 1990 v o t v mp, 1990 l 770 p q p o l. eq l 1996 l 123 p p o 1997 e o v eq l 2000 l 465 p o lp, e 2002 l 2 p op l. (3) op o Fig. 3p ˆ o r~ o (9,641 ) op l o 7o v, op rp p plp, 1,912 p o l r~ o p k 20% v p. op tp 1o p 576 p o mp, { e pm m d Fig. 5. op o ( ). 418 229 p o l 2om 3o v m. (4) r (IPC) o 1981 2002 v m p,, o l o 9,641 p ˆ o r (IPC), r~ o p 50%l 4,844 p o 10 p l, t q pp p v p D01F(ps, o, p r sl pl r vp ;ˆ rsl r q ) r~ 9,641 t 1,405 p v m. 3.1.2. (1) o l o Fig. 4 1981 q v l o 339 p ˆ o o l p 20l p o p Š p. 1980 (1981-1990)l o m 1990 (1991-2000)l o 1980 l 73 p o p 21.5%, 1990 238 p o p 70% v pp
46 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) 43-51 Table 2. tn opp o ( ) '81 '85 '86 '87 '88 '89 '90 '91 '92 '93 '94 '95 '96 '97 '98 '99 '00 '01 Mitsubishi Rayon 1 3 1 2 2 1 1 2 13 Toray 1 1 1 1 2 4 3 1 2 16 Saehan 1 1 2 3 3 1 11 POSCO 1 2 3 4 1 11 RIST 1 1 3 1 1 2 1 10 Daewoo Heavy Ind. 5 1 1 2 9 Dow Chemical 6 1 7 Fig. 6. r o p( )., 2000 p 28 p 8.5% ˆ o r~ p r. p l o ˆ o 1990 l o lpp ˆ, p e l ˆ o p q l lpp p. (2) op o l o ˆ op tn op p, Fig. 5 m p p lp { e pm p 13 jp q p op m, p, d, l l p 11, 11 10 p p p. p p { e pmp n Table 2l ˆ p o 13 t 10 p 1980 l o p 3 p 2000 l o 1990 l l o v kk. v, l p nl 1990 q v l p v kv t o p p k pp, n t lp 1995 o 5 p p v p k 1990 t p l p ˆ o l l q mpp k p. (3) r o Fig. 6p l o ˆ o p opp p n pp, n p opp e r ˆ p. r~ op t, n pp v pp 53% 47%p p o p p tp v p p ˆ. n p op pp r e l p p 31.3%m 15.0% v m, pp m, d, dod p o Fig. 7. ol o (p ). p op pp ~ 6% p ˆ, p p o ropp n pp k pl. 3.1.3. n (1) p ( ) o l o Fig. 7p 1981 q v p l o 7,680 p ˆ o o p ˆ p. p p n 1990 p tp p ˆ p vp o 4,769 p r~ o p 62% v p. 1994 1996 v 3 k o 149 p tl 1997 e o l p ˆ l. ( ) op (p ) Fig. 8p 1981 2002 v p l o ˆ o op, o 7 p p p ˆ., r~ ˆ o o p 7,680 p 22%l 1,680 p p 7 l p o l. o q p r~ p 6.2%l 479 p o p mp,
Carbon Fibers (III): Recent Technical and Patent Trends 47 Fig. 8. op o (p ). Fig. 10. op o ( ). Fig. 9. ol o ( ). { e pm, k m d p 357, 210, 203 p p. (2) ( ) o l o Fig. 9 1981 2002 v l o 986 p ˆ o o l ˆ p. p n 1980 l 391, 1990 l 589 p o l pr l vt op v k pr o o v, 20l l ~ t o p. p p p n ˆ ol l r l p lv p k t v rp p lv ppp lt p. ( ) op o Fig. 10p 1981 q v l o 986 p ˆ o op, o 7 Fig. 11. ol o (o ). t 7 p p p ˆ p, r ~ ˆ o o p 986 p 9%l 89 p p 7 l p o l. o q p r~ p 3.1%l 31 p o p mp, { e pm m 23, 18 p o l 2om 3o v p. (3) o ( ) o l o Fig. 11p 1981 2002 v o l o 636 p ˆ o o p ˆ, o p n p l qv v 20l k p rn o v p p ˆ p., 2001 l 46 p o l, p p 1980 o l p 5 v p.
48 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) 43-51 Fig. 12. op o (o ). ( ) op o ˆ ol o p op o p p, v Fig. 12} o 7 o 139 p ˆ o r~ 636 p 22% v p. 139 p 81%l 113 p p l p o p, t q p o opp p p p 53 p o m. 3.1.4. ˆ o q o 2006 p ˆ o q l o 7 p p p ˆ o pƒ, o,, n r l Table 3l ˆ l. r~ 98 t ˆ o l k 9%, d v 12%, t q 3%, q 24%, 16%, ˆ 36% ˆ p, o q p pƒ ˆ om v Fig. 13. ˆ o q r m (X : op, Y : o, o: op t, / /p /o, '05~'03, '02~'00, '99~'97... '75~'73, ~72) p, j e pm, Š d r~ o p 65% v m. 3.2.1. ˆ o r m p ˆ o e l o (Y ) m op (X ) p l, o p r Žk m p, op m o v r, op kr o Table 3. p ˆ o q (2006 ) «ƒ l l l y n ƒ¹ n ƒ¹ «Toray 2 4 3 6 5 18 38 Mitsubishi Rayon 2 4 0 4 3 1 14 Toho Tenax 2 1 0 2 5 2 12 Teijin Techno product 3 0 0 0 1 1 5 Honda Motor 0 0 0 1 0 2 3 Mitsubishi Heavy Ind. 0 2 0 0 0 0 2 Mitsubishi Eng. Plastics 0 0 0 2 0 0 2 Etc. 0 1 0 8 2 11 22 9 12 3 23 16 35 98 p(%) 9.1 12.2 3.1 23.5 16.3 35.7 100
Carbon Fibers (III): Recent Technical and Patent Trends 49 Fig. 14. ˆ o q l n p rop (X : ol, Y : rop, o: op t,, ~'95, '96~'98, '05~'07). Table 4. vl l t v ~1987~1990~1993~1996~1999~2002~2005~2007 n 1 1 6 4 46 39 9 106 e p} 3 4 7 r 2 13 41 8 64 2 1 3 t 1 12 13 2 2 1 13 53 23 90 ~ 2 2 ~ 11 15 13 39 r 4 6 4 14 r 1 1 2 7 14 3 14 2 40 1 2 3 1 8 22 13 94 188 59 385 * o : op t,, ~'87, '88~'90, '03~'05, '06~'07 * op n rp op 18 op l p l l 06~ 07 o l p r~rp r m v., op m o s p l r Žk l Fig. 13l ˆ Fig. 15. p vl v. l. ˆ o, q rs k l 1990 o op v p ˆ, q ˆ o ql l p v p r l p p Ž. 3.2.2. p vl r p t opp e l vl o, n p r, v p l vl Žk m. Table 4l ˆ m p vl l p, 1990 rp o p eq lp, 2003 ~2005 l op q p l. vl ne p op q kp, ˆ op p r p 6o v p p s l. Fig. 14 ˆ op l n pp o p ˆ p, 2001 v n r opp o pp 30%r v mp, 2002 p n p p op v l 2005 p 40% p v p ˆ. p ˆ o q p o n l p eqp r o n l o p v eˆ l p Ž. Fig. 15 ˆ o q rs r~l r vt o v (Activity Index) vl e p p 1 nl r p p p., tm p vt q kp, vl v p 6.2 q k p n p k pp, pp r rp 4.8 4.2 ˆ l.
50 Min-Kang Seo et al. / Carbon Letters Vol. 10, No. 1 (2009) 43-51 Fig. 16. p tn Ž (X : op r, Y : Ž /Ž ). 3.2.3. p eq Fig. 16p t p op r Ž m Ž p. p rp Ž p l,, n o p r l p ˆ, Ž o, p eq p ˆ v n., p Ž Ž ˆ kl p eq p v o l p q p v p Žk p. 3.2.4. PAN ˆ ol tn op PAN ˆ ol tn opp k r v ˆ o l tn e lp p m j e pm v m. p l o l p '76 ~'06 v 314 p o mp, p v 279 p o p p tn ˆ eqp p p ˆ p, l l rp 1997 2006 l 2 p o m. j e pm l o l j e pm 75 ~ 06 v 254 p o mp, o p p 230 p p o pm v p p tn eqp r mp, l l rp op 1987 1993 l 2 p o m. p e opp o ˆ o rs o r ~ p v mp, pp ˆ l 81 p v m. 4. l 1981 2000 vp p,, o l o ˆ o l p q m. o, p p r ~ o p 79%l op mp, o, p 10%, 7% 4% v m. p} o l k p p ˆ o l p l o p l p p o p r rp o p ˆ o l o p Žk pp, ˆ o p v r Ž k p. o o l p, 1980 l o kp 1990 l o p ˆ p l e op l p p p, p p p l, nt rp n ˆ op n 1990 r~rp se mv, l ˆ op, p p e n p l špl q, s v p Š k, CNG, rn p, oe, p p p ~ l v l v k,, p n k, k e r or } k, p, p v, r r, l n p k l kl rnp p lv p. kp n k kl ˆ o o n p Ž l 1990 l t l p 2000 p l n n p ˆ p p., ˆ o q rs k o op v r l r p p k Ž, eq re ql p q o kl op re n. p p p pr l p e n, pl, l r p vop p lrk p Ž. p lr ~ p n qp p p e q 7s o l p ˆ q eql ˆ l p n k p. m l o p vop 21 Ž ll l ( l v l )p p p ld. y [1] Donnet, J. B.; Bansal, R. C. Carbon Fibers, Marcel Dekker, New York, 1984S 125U
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