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1 Carbn Letters Vl. 9, N. 4 December 2008 pp Studies n the Stabilizatin f Rayn Fabrics fr Preparing Carbn Fabrics: 2. Fast Isthermal Stabilizatin Prcesses at High Temperature Sung Bng Yn 1, Chae Wk Ch 1, Dnghwan Ch 1,, Jng Ky Park 2 and Jae Yel Lee 2 1 Department f Plymer Science and Engineering, Kumh Natinal Institute f Technlgy, Gumi, Gyungbuk, Krea 2 Cmpsites Research Team, Agency fr Defense Develpment, P.O.Bx 35-4, Daejen, Krea [email protected] (Received September 3, 2008; Accepted December 9, 2008) Abstract In the present study, fast isthermal stabilizatin prcesses fr rayn precursr fabrics were perfrmed at 350 C and 400 C within 3 minutes and the chemical and physical characteristics f the stabilized fabrics were investigated. In additin, rayn precursr fabrics were pre-treated with three different phsphrus-based flame retardants and then stabilized. The effect f flame retardants n the chemical cmpsitin, thermal shrinkage, weight change, thermal stability and XRD results was examined, cmparing with thse f the precursr fabrics. The result shwed that the stabilizatin f rayn fabrics was mst effective as the stabilizatin temperature was 350 C, the stabilizatin time was 3 min, and the pre-treatment with phsphric acid f 1 vl%. The carbn cntents f stabilized rayn fabrics were increased with increasing stabilizatin temperature and time, whereas the xygen cntents were decreased. Als, it is likely that the pre-treatment with phsphric acid plays a rle in retarding the change f chemical structure f rayn fabric. The XRD result was quite cnsistent with the result shwing the effect f phsphric acid n the chemical cmpsitin, thermal shrinkage and weight reductin f rayn fabric. Keywrds : Rayn Fabric, Isthermal stabilizatin prcess, Flame retardant, Pre-treatment, Characterizatin ˆ (carbn fiber) pm(rayn), k (plyacrylnitrile: PAN), (pitch) s p ƒ rs p l q r q l l r1 ˆ p pm ˆ ƒ rs ˆ r p r l v [1]. pm ˆ lr n k l l p n k r p v q q p d p jp vmp r p sk nt qn m l q p q v v n n l n p [2,3]. pmv (rayn fabric)p p p kr r(stabilizatin prcess) ˆ r(carbnizatin prcess)p s ˆ v r p. ˆ v p p ˆ p p n eˆ l 2500 C p l q p t l r(graphitizatin prcess)p ˆ ˆ llv p [1]. kr rp PAN ˆ l l rp l} p, rp ˆ rs q tn rp v v k. srp llv ˆ p r, r p lr, r p ˆ ƒ (precursr) s, kr r s l v pql ps.. kr p s, s, r, lr r p ˆ p l n tn l p. kr ~ ˆ r r rl ƒ p r, r lr p [4,5]. pm ƒ l p n e, ƒ ˆ p p n. p rp l} m p dm p l sq ˆ p v p. p rp 400 C p l t k r r t 200 C p l m kvl p p v p v p,, kn v p t [6,7]. pm p l t 350 C~400 C pl [8-10]. pm ƒ p sp p m p l v p v s v., d n sp m l n v pl vp p. p pmv p t kr rp 400 C v m v eˆ v, p p mlp l p. ~w v qp 250 C p ml,

2 Studies n the Stabilizatin f Rayn Fabrics fr Preparing Carbn Fabrics: 2. Fast Isthermal Stabilizatin Prcesses w rp v m l p q pl 250 C~350 C ml, w t m 350 C p p mlp. p rp w mll v p r~ v p k 80% p p e p. p r, r rm m re l m p. v p kr m mll r, r v, p m mll rp v. p m mll p l} r s p rl v p rl kr rp ep p [11]., l l pm ƒ v l kr rp e(batch-type) p m. v, 400 C v m m rp p k, kr m 350 C 400 C reˆ wp e k l} e p eˆ m kr r p n m. e l m kr rp tn rp rp p 350 C~400 Cp kr m l 3 p l pmv l l kr rp v mp l v r r s l, ml m k r rp rn p ˆv p. kn, lr n l r} kr pmv p s, l, t, lkr sl lrp m p s mp, pm ƒ v m. x l l p Acrdis l rs pmv (Acrdis T-700)p n l kr rp m. kr r k pmv p t, v kr p lkr l r} p m p s l kr rp rl p p s p p lr pmv p p } m. v, p (phsphric acid, H 3 PO 4, (t)), 3-(hydrxylphenyl phsphinyl)prpanic acid (HIRETAR-205, H-205, (t) KOLON) (Fig. 1), FR-SH(Flame Retardant-Special Hard) (ˆ l ). ~w, p p q k v l t p, l nkp t l n m. w, H-205 l ql ld l n p lr r p pp k 14% p p [12]. n p ml p l p lr p k r p. w, FR-SH q qn pqƒ n ln ld v l n p m lr Œ n k~p r p n l p ˆ., r} e p r p m} r l p sp p k r p. ph 6.4 ~ 6.6p, k k p pm vp v p. pl s r v kk. yw e l n pmv p 50 mm, 60 mm v kp r l t m. t v p H 3 PO 4, H-205 FR-SH s p lr 1vl% j nkl l p pƒl v l ml 60 k dip-cating eˆ 80 Cp m l k 6e p s m. 1 vl% p np prp l [13]l pm p kr l p lr p m p s, 1 vl%l q n ˆ l p. lr } r p pmv ˆ kp, } r k p v p } l p p vlv p p l. lr } p m p l r} v kp pmv p t l kr rl n m. yœ pmv p kr rp kr n l p r kp p p 50 cc/minp pr t p m. r eq r pr t pmv p lž l m kr p l l l l. kr m 350 Cm 400 C reˆ (furnace) l pmv p e p 30, 1, 2, 3 j e wp e k m k r rp v m. kr rp r} v k p pmv s p lr n l 1vl% } pmv l l p m. m kr r r l pmv p m t r m. p Fig. 1. Chemical structure f 3-(hydrxylphenyl phsphinyl) prpanic acid used in this wrk. kr rp r l kr l pmv p t r q v rp

3 310 Sung Bng Yn et al. / Carbn Letters Vl. 9, N. 4 (2008) rnp n l s m. v p l p kr r r v p, m. pmv ƒ, kr rp llv pmv l s p s l (elemental analyzer, Elementar Vari EL, Elementar Analysensystem) n m. e 1150 C r p ml l l e d l C, H, N, S O p m. (O) p r~ 100%l C, H, N, S p p p p r m. p p np p ˆ p e m., p p p lr } e kr r l v l qs p p p p v kk. p l l p rp v tn p ˆ,, p s l p p. kr r r pmv p lkr l m kr e lr } s p m p s l lt (thermgravimetric analyzer, TGA 951, Du Pnt) n l 50 cc/minp s v d p l r m. TGA e p m 800 C v 10 C/minp dm s l m. pmv l l kr r s l X- r l X- r (highreslutin X-ray diffractmeter, X Pert PRO-MNR, Philips) n m. Scanning plp 2θ =5 ~50 step size 2θ =0.04 m. Step ne p 1m. l scan mde rn lp, n radiatinp K α p targeting q Cum. š e w Fig. 2 k 50 mm 60 mm p pmv l lr } r v k l 350 C()m 400 C (k )l 30, 1, 2 3 k kr e llv v l l kr l m t p r p. kr m l ~ me p v v p, m p l p l t pp v m. tlv ms l v p 37%, m p k 40% v l. kr m l v p p p v kkp, 350 C 400 Cl v p t n p ˆ., l} e p 3 p n 350 C l k 84% 400 Cl k 96%p e t m., kr r l l kp v p qlt p, 400 Cl 3 } 95% p Fig. 2. Thermal shrinkage and weight lss f the untreated rayn fabrics after stabilizatin prcess at 350 C (tp) and 400 C (bttm) fr different duratins in air. p t l v v k Ž l. m l 1 p p kr e l llv k 48%- 54%p t, pm ƒ p vp k r r tl l p t v v kkp, p s l v p kr p lvv kk Ž l. Fig. 3p s p p lr 1 vl% j pmv p r} p 350 Cl 3 k m kr rp, v p t pp r p. Fig. 2l kr m 350 C, 3 l m, lr } l lp kr v p l l p l p k 38% v, p l p 27% v tl lp p p pl., v p t p p n 80% 63% 17% kr. p p r} pmv p p p v p } v kp nm, kr r l v k k p p p. lr tl l t lrl p p rp

4 Studies n the Stabilizatin f Rayn Fabrics fr Preparing Carbn Fabrics: 2. Fast Isthermal Stabilizatin Prcesses p re p. Fig. 3p k 400 Cl 3 k m kr rp v l p. v p m t p 350 Cl m mp, r p pl., p p n v p l p rp p p s l. p 400 Cl p p l p p lt. 400 Cl s p lr t p p v p p t lr l q p p Ž l. p Fig. 2l 400 C, 3 k m kr lp re m p, k 96%l p e t p p p } l p r ppp p. e w Fig. 4 p 350 C()m 400 C(k )l Fig. 4. TGA thermgrams f the untreated rayn fabrics stabilized at 350 C (tp) and 400 C (bttm) fr different duratins in air, respectively. TGA measurements were cnducted in purging N 2 atmsphere. Fig. 3. Thermal shrinkage and weight lsses f the rayn fabrics surface-treated with different flame retardants f 1 vl% after stabilizatin prcess at 350 C (tp) and at 400 C (bttm) fr 3min in air. 30, 1, 2 3 k m kr rp lr r} v kp pmv l lkr p lt TGA p. l p 10 C/minp dm l 800 C v m. 30 k kr rp pmv p as-received ƒ pmv t p ltl. v, p m m e l p mv p r kr v kkpp p, v p p v l} rp v ˆm p p pl. ƒ kr v l pmv p p k Ë Ë Ëv Ë r p r rp l. 350 Cm 400 C l kr e p 3 v v l kr v p l kr p n l. TGA 350 Cm 400 C pl m kr e 2 p rl pm p r r

5 312 Sung Bng Yn et al. / Carbn Letters Vl. 9, N. 4 (2008) Fig. 5. TGA thermgrams f the rayn fabrics surface-treated with different flame retardants f 1 vl% and then stabilized at 350 C fr 3 min in air. kr pp q v pl pp ˆ p. v, l} rp pmv p 2 wp e l kr v l l p p r q mpp p. 2 wp l} e p pmv p kr l v k Ž l. kr e p 2 p p, 400 C p p ml l lkr p l. p 350 Cm 400 Cl 2 3 kp l} pmv p kr l m p t p rrp re l t p. e p TGA l} e p rp kr v l 300 C prl p lkr p l} e p wp p lkr k. p ~ e p lvl kr r t l p p, p p tlv l s l p pˆ l p. TGA r l n e l k 350 C p l 2 t kr pmv p l m ˆ l p p. Fig. 5 s p lr 1 vl% ƒ p mv l r} l 350 Cl 3 k m kr rp v l l s TGA p. Fig. 4l lt m, 100 C prl k 10% ~ 12%p t m k 400 C p l 2 t l. 400 C p p t pmv p kr r e m p l l v ˆ p eq p. H-205 r} kr pmv p 500 C prl lkr p q p p l. s p lr tl p p } kr v p lkr p rp p p s lp, Fig. 2 m 3l ltl p, kr rp pmv l l p l p p Ž l. rp lr } v k kr v } p, 350 C 400 Cl kr eˆ p, 3 p l l} e p kr v p p lkr p ˆ l. Table 1. A Cmparisn f the Chemical Cmpsitins Measured fr the Rayn Fabrics after Isthermal Stabilizatin Prcesses at Different Stabilizatin Temperature and Time and with Different Flame Retardants Sample C H O N S Precursr Rayn Fabric N Treatment (350 C), 30 s N Treatment (350 C), 1 min N Treatment (350 C), 2 min N Treatment (350 C), 3 min N Treatment (400 C), 30 s N Treatment (400 C), 1 min N Treatment (400 C), 2 min N Treatment (400 C), 3 min H 3 PO 4 1vl%, 350 C, 3 min, in air H vl%, 350 C, 3 min, in air FR-SH 1 vl%, 350 C, 3 min, in air H 3 PO 4 1vl%, 400 C, 3 min, in air H vl%, 400 C, 3 min, in air FR-SH 1 vl%, 400 C, 3 min, in air

6 Studies n the Stabilizatin f Rayn Fabrics fr Preparing Carbn Fabrics: 2. Fast Isthermal Stabilizatin Prcesses yw e w Table 1p ƒ pmv l v kr rp llv pmv l l n l s s lt. p kr r e r n lr } p, lrp s, kr m k r e p p s l m p lt. r, ƒ pmv p s p rp 54%, ˆ 39%, 6.4%, v 0.3% 0.3%p p s l. kr rp pmv l l p p, ˆ p v m. kr m } e p kr pmv p ˆ p n v, p n m. 350 Cm 400 Cl 30m 1 k l} n rn, rp lp kr v p ˆ p r s l k 60% ~ 78% p k 17% ~ 35% ˆ l. kr rl p m p, lr } v kp kr v p ˆ p } n p p s l., l} e p lv kr v p ˆ p v p m. p kr rp lr s p m p, H-205 } pmv p ˆ p rp, p p } p q p ˆ q p p ˆ l., p lr n 3 k kr eˆ pmv p m 350 Cp n 400 Cp n p ˆ p p ˆ l. p llv s p, tl kr rp pmv l l p p tp el ˆ p v eˆ lr r} v k 400 Cl l} p v p Ž l. pmv p p lr } n ˆ p rp ˆ p lr kr rp ve rp p p l l p l r ˆ p r e p l kr l p e p tltl p p. e w Fig. 6p ƒ pmv l XRD p. k l 2θ =22 p dp mnclinic unit cellp (002) p p p. k 2θ =16.5 p q p mnclinic unit cellp (101) p ˆ. 2θ =22 pl p k 2θ =20 p unit cellp (101) l p ƒ pmv p p d II r s p p p ˆ [14,15]. Fig. 6. XRD diffractgram f precursr rayn fabric. Fig. 7. XRD diffractgrams f untreated rayn fabrics stabilized at 350 C fr different duratins in air. Fig. 7p 350 Cl 30l 3 v kr e p e ˆ rp lp pmv l XRD lt. v l lr } v kk. kr r e p lv m l p 2θ= p r tl lpp p p. 2 p m kr e p r. XRD p lv p r p p, p d sl v tl e l p. v, rp kr e l pm ƒ v p r rp r s kr rl p Ž e q dp 6 p s s s eq kr s p ˆ

7 314 Sung Bng Yn et al. / Carbn Letters Vl. 9, N. 4 (2008) Fig. 8. XRD diffractgrams f rayn fabrics surface-treated with different flame retardants f 1 vl% and then stabilized at 350 C fr 3 min in air.. 30m 1 p wp re p n m l 2θ= p m s p n ˆ. p ƒ v p p p pm p p m m e s l dp r rp r s v ppp m l ˆ., 2θ= p v m p skv s v p kr v r l} rl pm p r r v m p p p. kr r l m dp r s p Ž. Fig. 8p p, H-205, FR-SH s p lr 1vl% l r} l 350 Cl 3 k tl kr rp pmv p XRD lt. kl l m l p, 2θ = 16.5 ltl mr p rp, 2θ =22 r~rp t l l. p p nl p 2θ =22 H-205m FR-SH l rp ˆ. p p p pmv p } p pmp r s m v l p Ž. p p p } kr r e pmv p s p s vleˆ l p mpp lt p. pm p XRD kl l s l, t l p p m l m p. s p p lrp p, H-205 FR-SH r } pmv l l tl m kr r rl l} l v p l t pp s, kr m 350 C, kr e p 3 1vl% p p } pmv p kr l q plpp p m. r} r v kp ˆl v p kr lr r} p, 350 C 400 Cl kr eˆ p, kr e p kr v p p lkr p ˆ l. kr rp pmv l l p ˆ p kr m 350 Cp n k 73%, 400 Cp n k 78% v v mp, lr r} nl kr pp vl ˆ p k 61% ~ 63% v r l. kr m } e p kr pmv p ˆ p n v, p n m. kr rp pmv l l p p tp el ˆ p v eˆ lr r} v k 400 Cl l} p rr p s l. pmv p kr v v kp r l ƒ p p d r s p l. kr r e p lv m l p 2θ = p r t l l. 350 Cl 2 p m kr r e p r. p } kr r e pmv p s p s vleˆ l p p Ž l. l l p l vl p lp pl. š x [1] Bahl, O. P.; Shen, Z.; Lavin, J. G.; Rss, R. A. in Carbn Fibers 3 rd Ed. (Dnnet, J.-B.; Wang, T. K.; Peng, J. C. M. Editrs.), Marcel Dekker, New Yrk, 1998, Chapter 1. [2] Bacn, R. in Chemistry and Physics f Carbn, Vl. 9 (Walker, Jr., P. L.; Thrwer, P. A. Eds.), Marcel Dekker, New Yrk, 1973, 1. [3] Peebles, L. H. in Carbn Fibers: Frmatin, Structure, and Prperties, CRC Press, 1995, Chapter 2. [4] Tang, M. M.; Bacn, R. Carbn 1964, 2, 211. [5] Bacn, R.; Tang, M. M. Carbn 1964, 2, 221. [6] Brid, A.; Nelsn, M. A. Cmbustin and Flame 1975, 24, 263. [7] Jnes, B. F.; Duncan, R. G. J. Mater. Sci. 1971, 6, 289.

8 Studies n the Stabilizatin f Rayn Fabrics fr Preparing Carbn Fabrics: 2. Fast Isthermal Stabilizatin Prcesses [8] Lipska, A. E.; Wdley, F. A. J. Appl. Plym. Sci. 1969, 13, 851. [9] Duffy, J. V. J. App. Plym. Sci. 1971, 15, 715. [10] Shafizadeh, F.; Bradbury, A. G. W. J. Appl. Plym. Sci. 1979, 23, [11] Ch, D.; Lee, J.; Park, J. K. J. Sc. Adhesin Interface, Krea 2004, 5(3), 10. [12] [13] Yn, S. B.; Ch, D.; Park, J. K. Plymer(Krea) 2005, 29(2), 211. [14] Basch, A.; Lewin, M. J. Plym. Sci.: Plym. Chem. Ed. 1973, 11, [15] Kumar, K.; Saxena, R. K.; Kthari, R.; Suri, D. K.; Kaushik, N. K.; Bhra, J. N. Carbn 1998, 36, 1842.