Korean Chemical Engineering Research

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(1)Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005, pp. 53-59. + /·§ ¿ô§ O¿5 K§ ;·. < L ÜK? g k{Ø* ÏÐ|*. ,†. KhêH,¬õgò h à_õgz _,¬õg« 136-791 ÖQ {g GöË 39-1 *ã¬HG dà@àHê 121-742 ÖQ K¯g U¤ 1 (2004¸ 2ö 24³ [¤, 2004¸ 11ö 12³ >) A Study on the Electroplating using Macroemulsion in High Pressure Ji-Young Park, Jun Youl Yang, Dong Jin Suh, Ki-Pung Yoo* and Jong Sung Lim*,† Environmental & Process Technology Division, Clean Technology Research Center, KIST, 39-1, Hawolgok-dong, Sungbuk-gu, Seoul 136-791, Korea *Department of Chemical and Biomolecular Engineering, Sogang University, 1, Sinsu-dong, Mapo-gu, Seoul 121-742, Korea (Received 24 February 2004; accepted 12 November 2004). ß È. á õgÑ2 ª

(2) l fõ «ÄGñ ð»ª«d!Q MgU k¿³ÑÓs K á ê {s g MQE ð»ªÑÓ Mgs ¤}G. ª

(3) l f³2 n«d!,Q n¤,õ QÑ (r sodium salt of bis (2,2,3,3,4,4,5,5-octafluoro-1-pentanol) sulfosuccinateõ ÄGk (+)ê (−)k³ n-¶ê g-¶s ÎÎ ÄG. ð»ªk¿³ÑÓ =Ñ ê n-,

(4) ê ,Ê F =Ñ ê n-,

(5) s 9Gg á ê «d!/n-U k¿³ÑÓÑ g ê n-,

(6) o ,Ê örÑ K aÝ

(7) è³G. ª

(8) l f Q U « Ñ Âj2 s oÝ, .Gñ UÑ ÍK ª

(9) l f õ 2, 4, 7 wt%³ ¡dQZk ä¯ Ñ ó(G2 U z)õ 10 vol%Ñ 70 vol%>( ÍQZ. -Ê õ s <4Ý, .Gñ ð»ª«d! ¬UÑ é³¶s ÄGñ êõ oÝI. k¿³ÑÓ « æ2 « Ñ2 ª

(10) l f Í 40¤´ MÍ

(11) ê æ2 n- « H ÝGk, U z)Í ÍO¤´ MÍ

(12) ê M,MÍ 4(Ê æ2 n- « ÍG. K, õ Î, é ³¶Ý «d!Í Î¤K Áêõ Ý»s < ¤ ÀÉ. Abstract − In this study, the supercritical electroplating was investigated by forming macroemulsion of electroplating solution using surfactant in supercritical CO2. The fluorinated analogous AOT surfactant, sodium salt of bis (2,2,3,3,4,4,5,5-octafluoro-1-pentanol) sulfosuccinate which has both ‘CO2 philic’ chains and ‘hydrophilic’ head group was used as a surfactant, and Ni plate and Cu plate were used as the anode and the cathode, respectively. Electroplating was carried out in the conventional method and the supercritical macroemulsion and both results were compared. The supercritical electroplating was carried out in various concentration of surfactant such as 2, 4, 7 wt%, the volume ratio of Ni-plating solution to CO2 was varied in the range of 10-70 vol%, and propane was used as a supercritical fluid instead of CO2. According to the experimental results, the plated surface of Ni on Cu plate performed in supercritical macroemulsion was better than that, in conventional state. In the image of Ni surface plated on Cu plate in supercritical state, there were fewer pin-holes and pits comparing with that in the conventional process. The current and conductivity was increased as the volume ratio of Ni-plating solution to CO2 was increased and the current and the amount of Ni plated on Cu plate were decreased as the concentration of surfactant become higher. In addition, in case of the continuous phase, using CO2 was more effective than using CO2. Key words: Supercritical Electroplating, Ni Plate, Cu Plate, Macroemulsion. † To. whom correspondence should be addressed. E-mail: [email protected]. 53.

(13) 54. 1.. C «. á(öCùö,öK,>ö»Ü . §, Ë´ h éfÑ ¬K î[k³ ð»ªKõ ÄK õ g K _,¬s @GÊ ÀÊ Ä ~t nh J¯ à _k³ ¡dg ÍÊ À. U¾, ñ6 K yÑ ð»ªK ß Ys Q« Í@Ê À2 ð»ª«d!õ «ÄK õgÍ G j Q« «P´@Ê À. «6K õg y G÷³ _,¬« É h ndJ¯ à_k³ õgæÊ À2 a« ‘ð»ªÑÓ M g à_’«. o ,

(14) Ñ ñ 2 Y o @s ½¾2 ÆÊk³ à_o f\@ MÜ à_Ñ g¢G @\Ñ ßR ê R Ùs zñGñ MÜ f\ z ÍÍjõ åK¾ ³ ¤ À2 kÎ y®K à_«. 6÷ «6 K à_o ¿Ã, Ãr, Q8dg- Ù ÎÜ à_ á æ2 Cr , CN, Pb³ ¯g ¯Ñ jJ³ O 4n¶ ¤H Ú h Ñ KgK ¬,J¯ à_Ñ K. «³ ¯g KgK Us _dG, .Gñ L~-, ô, Â@í s- Ù K ~tÑ õgQ ôts ,Ö«Ê Àk÷ U _dQ « Ñ ¤äæ2 fJ¯ +

(15) s QÑ £ÇQÿ@ \GÊ À2 Y _Ñ À. U¾, h Æ2 §Gñ Y×YJ¯ õg êOk³ _ ,¬9õ ä,Ñ2 YHJk³ ´sÒ z «. «6K à_ éfõ gG, .g ,Ê à_s í K õgÍ ³á Yoshida Ù[1-2]Ñ g f8ê ‘ð»ªKõ «ÄK Mg’«. ð»ªKõ «ÄK Mgà_o Uê ð»ª«d!Ñ k¿³ÑÓ(macroemulsion)s QE Mgs G2 à_ k³ ð»ª«d!2 Uê HYæ@2 :@O

(16) ª

(17) l fõ ÍWk³ k¿³ÑÓdÍ ÍDG2 aÑ ô8, k ¿³ÑÓs Q á Mõ 0MGñ « è³Gj «P ´@´ G2 öR«. « à_o ð»ª 2 4»ª íH, õ Ë´ ð»ª «d!õ «Äg Î s- à_s 8MGÊ YJ«Ê UGj YQO ¤ Àk §tUê U Ù Ä

(18) s µfG³ ÊÆÑ è@G2 U

(19) s QÝGñ h 1 s ö@O ¤ À. 6³ ÊÆh í, @ -Ê U é«Äs HO ¤ À. \HÑ2 ) Þt« 9uJk³ æ´ Î¤K êõ »s ¤ À. «6K õg2 «Â ,Ê øé[3-4]s 0Gñ FÑ YQæ2 à _Ý Î¤K Y« e¯æÉk «Ñ ¬K MJ ÆQs e?G , .K õgÍ ª D}«. á õgÑ2 n«d!,Q n ¤,õ QÑ @r sodium salt of bis (2,2,3,3,4,4,5,5-octafluoro-1pentanol) sulfosuccinate (F-AOT)õ ÄGñ ð»ªÑÓ =Ñ s K á «õ ,Ê örÑ K êQ 9GGk ª

(20) l f , «d!Q U z)9 Ú «d!Q é³ ¶ Ù õ Ñ !ñ Áêõ e¯G. 21. +6. 2.. ¿ «. /·§£ O{O k¿³ÑÓ ¬M,M2 Bruggeman[5]Ñ g f8ê H1RÑ g ªGÊ n-U z)õ 10 vol%Ñ 90 vol%(mole fraction; 0.1-0.9)>@ ¡dQZk ªRo {ê ç. 2-1.. ¤@¤ C43× C1 2005 2. σ ------ = ( 1 – φ )α σm. (1). 2 «d! z)~S, σo k¿³ÑÓ M,M, σ o õ (continuous phase) M,M, σ/σ 2 õ M, MÑ ¬K k¿³ÑÓ M,M³ ¬M,Mõ ÷Ê, α2 U_ ¤³ í-«d! k¿³ÑÓªÑ2 1.5õ ÄK. 2-2. ;Ø

(21) G H ´W£ Ïs Ï p£ û Mg« n-Uê «d!Q ço õ Ñ g k ¿³ÑÓ ÄUÑ ¤}î A, ¤ÄU¯ n-Uo M,Í ~í

(22) í« M,~gæ´ {ê ç« ,

(23) ê {,

(24) Ñ ÎÎ Q ¤Í è@K[6]. <ä> φ. m. m. 2. +2 Ni → Ni + 2e− 4OH− → O2 + 2H2O + 4e−. {ä>. <. Ni + 2e− → Ni + 2H + 2e− → H +2. 2. M,~g Mä>. <. 2H2 O → 2H2 + O2. {Ñ è@K ¤2 {,

(25) Ñ ´ -Lê )T ò¯ « æ³ ,

(26) k³z ¤õ fMgt è³Gj « ê. « A, ¤Q õ k³ Äæ2 «d!÷ ñ ÄkQ î îªõ ²5G, .g «Ë HYí ùòHJ Hs < 1®Í À. U¾, ¤Q õ («d! 2 é³¶)ê 2 ~ª H Yí »ª5(T )Q »ªFt(P )s ªGñ Y×ÆQÑ H Yí =õ ²5G2 a« y®G. Ö { RËÑ g HYí ùòHJ »ª Hs ªGÊ[7], « às ªG, .g 1®K ¨¤ ~ ùòHJ í j2 Table 1Ñ ÷É. cm. cm. 2⁄7 xiTci [1 – ( 1 – Tr ) ] Vm = R  ∑ ---------- ZRAm  Pci . (2). i. ∑ xiTRAi. ZRAm =. (3). i. xi Vci φi = ---------------∑ xi Vci. (4). i. Tcij = ( 1 – kij )( TciTcj ). 1⁄2. (5). 1⁄2. 8 ( VciVcj) 1 – kij = ------------------------------1⁄3 1⁄3 3 ( Vci + Vcj ) Hankison-Brobst-Thomson(HBT). ê ç« Þ ¤ À[8].. (6). RÑ Äæ2 HYäko {. ∑ ∑ xi xj Vij Tcij *. i. j. Tcm = ---------------------------------* Vm. (7).

(27) ÊF k¿³ÑÓs «ÄK Mg. 55. Table 1. Thermodynamic properties of pure chemicals for calculating the critical Tcm and Pcm of mixtures Chemicals. Tc(K). Pc(MPa). Vc(m3/kg⋅mol). ωSRK. V*, L/mol. ZRA. H2 CO2 C3H8 H2O. 133.15 304.14 369.82 647.37. 1.29 7.37 4.24 22.031. 0.065 0.094 0.200 0.056. −0.23240.2373 0.1532 0.3852. 0.0642 0.0938 0.2001 0.0436. 0.3060 0.2722 0.2766 0.2338. 1 * Vm = --4. * *2 ⁄ 3 *1 ⁄ 3 ∑ xiVi + 3 ∑ xiVi   ∑ xi Vi  i i i. VijTcij = ( Vi Tci Vj Tcj ) *. *. ωSRKm =. *. (8). 1⁄2. (9). ∑ xiωSRKi. (10). i. ( 0.291 – 0.080ωSRKm )RTcm Pcm = --------------------------------------------------------------* Vm. 3.. (11). / . Fig. 1. The structure of sodium salt of bis(2,2,3,3,4,4,5,5-octalfluoro1-pentanol) sulfosuccinate.. 3-1. ÷ Z È Y×Ñ Äê n-U, «d! Ú ª

(28) l f Y Ñ. Äê Quo {ê ç. «d!(CO 99.99%, Æ, K h), 2,2,3,3,4,4,5,5-octafluoro-1-pentanol(F CH(CF ) CH OH98%, Aldrich, Âh), 1,4-dioxane(C H O 99%, Junsei Chem. Co., ³á), p-toluenesulfonic acid monohydrate(CH C H SO H·H O99%, Yakuri Chem. Co., ³á), sodium metabisulfite(Na H SO , a reagent, Aldrich, Âh), maleic anhydride(C H O 98%, Junsei Chemical Co., ³á), toluene(C H CH 99.8%, J.T. Baker), acetone-d (CD COCD 99.5%, Aldrich, Âh), water(Millipore water). n-U Æ o í 1 l ¢ dn-(NiCl ·6H O) 50 g, zdn-(NiSO ·6H O) 200 g, (H BO ) 50 g, carrier 10 ml, >f 2 ml, )Tö@f 1 mls Ê Ñ HYK. «A, o 323.15-333.15 K = íÑ ÏI Ä gK á HYK. n-UÑ zdn-o n-«5 cò0 ³ ÄæÊ, dn-o ~gõ ñDg ÄU M,M õ ÍQÿ2 òOs K. o U õ ÆQGñ n - ,

(29) s kHj G2 òOs K. 3-2. ¿§|g ´| Fluorinated analogues AOT ª

(30) l f¯ sodium salt of bis (2,2,3,3,4,4,5,5-octafluoro-1-pentanol) sulfosuccinate2 LiuQ Erkey [9]Q Eastoe Ù[10]Ñ g fQê Y rs ÞYGñ ÄGk ,Ê éËÑ æ´ À[11]. ª

(31) l f gÆRo Fig. 1 Ñ ÷É. 3-3. 5Ï O¿Sð£ Mgßj2 k¿³ÑÓ Æ, 5 +_ßj, Ft +_ ßj, Q0 c½ßj Ù 4Í@ z~k³ g æ´ Àk Î ßj Ñ ¬K É§K o {ê ç. k¿³ÑÓ ßj2 Ê F¯(z): 55 ml)ê ]5Æ³ g æ´ À. ÊF¯o «d! Q U« c½æ´ « «P´@2 Þk³ )º¯-)ãs. ÄGñ 35.0 MPa>@ ¤ À´ fÊæÉ. ¯o M

(32) z, yJz, á

(33) z «Ñ ÎÎ ·Q ê ºé· YCéõ ½GÊ åTQ wT³ Æ?G. ·Q o k¿³ÑÓ« æ2 2. 2. 2 3. 2. 4 8 2. 3 6 4. 3. 2 2. 2. 5. 4 2 3. 6 5. 3. 6. 2. 3. 2. 3. 4. 3. 2. 3. Fig. 2. The apparatus of electroplating using supercritical macroemulsion. 1. High pressure reactor with view-cell 9. Magnetic stirrer 2. Cathode (Cu plate 1×2 cm2) 10. Pre-heater 11. High-pressure pump 3. Anode (Ni plate 1×2 cm2) 4. Voltammeter 12. Continuous phase cylinder 5. Pressure transducer 13. Ni-plating solution reservoir 6. Precision pressure indicator 14. Vacuum pump 7. Pressure generator 15. Thermostatic air bath 8. Thermocouple. Ú « æ2 ê_s L8k³ îûG, .Gñ ãd K-õ. ÄG. ]5Æ 52 ]5Æ z à,Ñ g K@ê . ÊF¯ z GÑ .jK 5 +_ßj2 I]5«õ @¥ 5 ª+,(model F250 MkII, Automatic Systems Laboratories Ltd., U.K)Ñ õGÊ, 1ó2 0.01 C«. ¯ê õê Ft +_ßj2 0.1 MPa« +_ê Fto @¥ Ft@Qª (Model XPM60, Beamax, Finland)Ñ Mæ´ ,Qê. Q0 c½ ßj2 õ ê U« c½æ2 2z~k³ g æ´ Àk ¯ +

(34) Ñ c½zQ õê ÊF Béõ ÄGñ òG2 Ft>@ c ½K. ð»ªÑÓ Mg ßj2 Fig. 2Ñ ÷É. 3-4. O¿SG` g-¶ .Ñ ð»ªk¿³ÑÓÑ K n- Mgo { o. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

(35) á(öCùö,öK,>ö»Ü . 56. ê ç« ê. MgÆ Ñ ¯ n-¶(10 mm×15 mm) ê {k³ g-¶(10 mm×15 mm)s g9GÊ ¶ « Mõ 15 mm³ Ê_K. ¶ê {¶Ñ õê Mo ÑÓê M,Í 0G@ :´ ,

(36) Ñ ºñ· `õ öî QõQ. Æ2 DàBéõ «ÄGñ z ¨ís fMK á n-U s c½K. «A, n-U Ñ ³_

(37) ª

(38) l fõ Ê « d!(2 é³¶)õ ÊFÄ Béõ «ÄGñ c½K. -Ê Æ «d!Q n-Us K Gä,õ «ÄG ñ HYK. Gä« QÊæ

(39) Yó & íHo k¿³ÑÓs G, QÊK. Gä á 30~« êG

(40) k¿³ÑÓ« UMGj æÊ Æ2 ]5ÆÑ g ³_K 5³ K@ê. òG2 5 Ú FtÑ «í

(41) {Ñ (−) MÍQ Ñ (+) MÍõ õG ñ M,õ 0Gj K á Q. « ³÷

(42) «d!Q Us Æ âk³ QÿÊ « ê ¶ ,

(43) s í³ RGj §tGñ ª

(44) l f÷ ¨ís fMK á QÆQ. 3-5. /Ü§ ? £§ O¿S á õgÑ ¤}K õg Äo {ê ç. ~, ÊF = ð»ª«d! k¿³ÑÓs «ÄGñ s GÊ «õ n -,

(45) è³ Ñ ¬g ,Ê F =Ñ ê êQ 9G G. .~, ª

(46) l f ¡dÑ !ñ MÍ §,õ QÑÑ !¶ +_GÊ ÎÎ Ñ ê n- s +_ G. »~, U z)õ 10 vol%Ñ 70 vol%>@ ¡dQ á U z)Ñ !¶ ~í2 MÍ §, Ú ê n- s oÝI. ¨~, k¿³ÑÓs G2) õ k³ Ä æÉ «d! ¬U é³¶k³ ÄGñ õ ¡dÑ !ñ Áêõ oÝI. 4.. û G. «d!/n-U k¿³ÑÓÑ Mgs ¤}GÊ, «õ ,Ê ör¯ FÑ K êQ 9GG. Fig. 3 o F(P=0.1 MPa)ê k¿³ÑÓ(P=10.0 MPa)Ñ ê n,

(47) s 600 ³ e¬K «Â@«. «d!Í Íê k¿³Ñ Óo «d! z)9Í 4 : 6«Ê, ª

(48) l f Í 2 wt% k, & Î H& 52 328.15 K«Ê, Ñ MFo 2.3 V ³ Ê_G. Fig. 3(a)2 ,Ê öRê ³K FÑ ê n-,

(49) « . n-,

(50) Ñ2 po -Lê )TÍ è@Gñ =Í DG@ :I. « Î2 FÑ « D}öÑ !¶ Mg Q n-U M,~gÑ g ¤Q Í è@GÊ U ¾ « «P´@2 { ,

(51) , g- ,

(52) Ñ è@G2 ¤ Í ¬³ ÍGñ z~Ñ2 « æ@ :, AéÑ -L ê )TÍ è@Gñ ,

(53) « Êí@ :o ak³ ê. 6÷ Fig. 3(b)õ Ý

(54) ð»ªk¿³ÑÓ =Ñ ê n-,

(55) o )TQ -L« M è@G@ :Ik ,

(56) « è³K as å ¤ ÀÉ. « Î2 è@K ¤Q õ k³ Äæ2 «d! DÄgtê Ê[K îw« À. «as ùòHJ¯

(57) Ñ oÝ

(58) , Fig. 4(a)-(b)Ñ Ý×« ¤+«d! HYí »ª5 (T )Q »ªFt(P )o Y×ÆQ(T=328.15 K, P=10.0 MPa) « G«. 6÷ ,Ê öRÑ g s G

(59) ¤+í »ªFt cm. cm. ¤@¤ C43× C1 2005 2. Fig. 3. The comparison of the surface of Ni plated on Cu (surf. conc. =2 wt%, ×600); (a) The surface of Ni plated on Cu in Ni-plating solution; T=328.15 K, P=0.1 MPa, (b) The surface of Ni plated on Cu in CO2+Ni-plating solution macroemulsion; T=328.15 K, P=10.0 MPa.. o MÆ Ñ U° Y×Ft(P=0.1 MPa)Ý Ê »ª52 ¤ Í 0.3259 mole fraction« s ÎÑO Y×5(T=328.15 K)Í HYí »ª5 « « ê. 6÷ Yf³ Y× ÆQÑ è @G2 ¤ o « Æ Ý o Æ s ÷, AéÑ Y ×52 »ªY Ý 4 HYí« ³ « 4r & k³ MGj æ´ Ägt 9s ,¬G,2 ´ . 6÷ ¤+« d! HYío »ª5Q »ªFt« Y×ÆQÝ 4 H Yí Æ 9Q îªÇ« M Æ Ñ U° ³ s «Pj æ ³ DÄgt« 9KÊ O ¤ À. Ö ¤Ñ ¬K ð »ª«d! Ägtk³ ¯g =Í kÎ Dg@2 a s < ¤ ÀÉ. {o ª

(60) l f Í Ñ Âj2 s oÝ, . Gñ ª

(61) l f õ 2, 4, 7 wt%³ ¡dQEÍ

(62) QÑÑ ! ñ MÍ

(63) ê g- ,

(64) Ñ æ2 n- s oÝI. Uê «d! z)9õ 3 : 7³ GÊ, Y×52 328.15 K, F to 10.0 MPa =Ñ k¿³ÑÓs QZk MFo 2.3 V³ K@G..

(65) ÊF k¿³ÑÓs «ÄK Mg. 57. Fig. 5. The current passed with time in the various concentration of surfactant (2, 4, and 7 wt%) (T=328.15 K, P=10.0 MPa).. Fig. 4. Critical pressure and temperature of H2+CO2, H2+propane, and H2+water mixtures; (a) Critical pressure (Pcm) of H2+CO2, H2+propane, and H2+water mixtures, (b) Critical temperature (Tcm) of H2+CO2, H2+propane, and H2+water mixtures.. 2 ª

(66) l f Q QÑÑ !ñ MÍ §,«. êÑ G

(67) ª

(68) l f Í YY 4H¤´ ~í2 MÍÍ 4@2 as < ¤ ÀÉ. «ao ª

(69) l f Í 4@

(70) ÑÓ Y « K K« Yó .s@j æ´ ÑÓ Ñ õ4À2 n-«5 «Í .s MÍÍ 4@2 a k³ Ý¯. -Ê Mgä« ³´ÿ A QÑÑ !ñ MÍ ¡dõ oÝ

(71) « D}î¤´ MÍÍ YY

(72) Ñ ~í2 as å ¤ ÀÉ. «ao Mg« D}æ

(73) MgU « 5o {¶ .Ñ k³ hòæ, QÊG2), o QÑÑ Fig. 5. Fig. 6. The amount of Ni plated with the various concentration of surfactant (2, 4, and 7 wt%) (T=328.15 K, P=10.0 MPa).. !¶ YóJk³ ÍGÍ ³_QÑ« êG

(74)

(75) « ÍG@ :j ê. « Y× Î2 QÑ Ñ n-«5« hòæ2 « ª ÍGñ MÍ QÑÑ !¶ Ñ ~í2 ak³ Ý¯. Fig. 6o Uê «d! z)Í 4 : 6ê 5 : 5 ³ A ª

(76) l f Ñ !¶ ê n- s Ýñg. U« 40% ³ AÝ 50%³ A ê n- « QIk ª

(77) l f. Í 4PÑ !¶ æ2 n- « k´Ã2 as å ¤ ÀÉ. Fig. 5Ñ < ¤ À×« ª

(78) l f Í 4H¤ ´ d·hòæ2 n-

(79) « J´@, Aé«. 6³ ª

(80) l f o k¿³ÑÓs Q ¤ À2 p. Ñ M

(81) s Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

(82) 58. á(öCùö,öK,>ö»Ü . Fig. 7. The average current passed with the volume of Ni-plating solution (T=328.15 K, P=10.0 MPa, surfactant conc.=2 wt%).. Fig. 8. The amount of Ni plated with the volume of Ni-plating solution (T=328.15 K, P=10.0 MPa, surfactant conc.=2 wt%).. ÄG2 a« K-O ak³ @Îê. Fig. 7-8o n-Uê «d! z)9Ñ !ñ ê õ ÷É. 52 328.15 K, Fto 10.0 MPa, ª

(83) l f. Í 2 wt%³ A k¿³ÑÓs QZk MFo 2.3 V³ Ê _G. Fig. 7o ÆÑ U z)õ 10 vol%-70 vol% ³ ¡dQ A 0Mæ2 MÍ §, èàs ÷. =Ñ Ý2 asF U z)Í Yó ÍO¤´ 0M ÁêÍ ¬æ ÉÊ, «Ñ !¶ I]« 4@2 as < ¤ ÀÉ. «ao Bruggeman Rs 0g < ¤ À×« U « Qs¤´ ~í 2 ¬M,MÍ @, Aé«. 6³ Fig. 8Ñ Ý2 a ¤@¤ C43× C1 2005 2. Fig. 9. The current passed with the volume of Ni-plating solution in Ni-plating solution+CO2, and Ni-plating solution+propane macroemulsion (T=328.15 K, P=10.0 MPa, surfactant conc.=2 wt%).. Fig. 10. The surface of Ni plated on Cu in Ni-plating solution+CO2, and Ni-plating solution+propane macroemulsion; (a) The surface of Ni on Cu plated in Ni-plating solution+propane macroemulsion, (b) The surface of Ni on Cu plated in Ni-plating solution+propane macroemulsion (T=328.15 K, P=10.0 MPa, surfactant conc.=2 wt%).. sF U z)Í H¤´ æ2 n- « ÍG. Fig. 9-10o õ k³ é³¶ê «d!õ Ä|s A, ~í2 MÍQ ê n-,

(84) s 9GK ê«. Y×ÆQo . ÎQ ³G. Fig. 92 é³¶/n- U k¿³ÑÓÑ n-Uê «d!Q é³¶ z)9Ñ !ñ è MÍ §,õ ÷ÉÊ, «õ ³K ÆQ «d!/n- U k ¿³ÑÓÑ +_K êQ 9GG. =Ñ Ý2 asF U z)Í ÍO¤´ ~í2 MÍÍ ÍGk é³¶«.

(85) ÊF k¿³ÑÓs «ÄK Mg. ÄæÉs A MÍ§,2 «d!Í ÄæÉs AQ M çI. M,J¯ +

(86) Os Êsg Ý

(87) , « & õ o ê_ Ñ MÍ ~ýÑ2 ³K Áêõ ÷É. 6÷ n-,

(88) è³ Ñ2 ñ êõ Ý. Fig. 10o õ « «d! Q é³¶³ A k¿³ÑÓÑ ê n-,

(89) s 600 ³ e¬K «Â@«. Fig. 10(a)2 «d!õ õ k³ ÄK Î ê n-,

(90) «Ê, Fig. 10(b)2 é³¶s õ k³. ÄK Î ê n-,

(91) «. Fig. 10(a)õ Ý

(92) O K ¬³ s O A è@ê ¤Í «d!Ñ Ägæ´ n-,

(93) « è³Gj æÉk÷ é³¶« õ k³ ÄæÉs AÑ2 Fig. 10(b)Ñ Ý2 asF è³K ,

(94) s ÷É. Fig. 4(a)-(b)õ Ý

(95) , ¤+«d! HYío Y×ÆQÑ ÎÎ Æ ê åî Gj ³ s K. ¤+é³¶ HYí Î2 Y×Ft (T=10.0 MPa)« & íH »ªFt(P )Ý @O è@G2 ¤ Í 0.1276 mole fraction «G³ A2 Y× 5Í HYí »ª Y «G ÆQ« ê. 6÷ ¤ è@

(96) « Ý2 J´ Y×ÆQÑ é³¶ê ¤Í & s G³ ÍÍK ¤2 -Lê )T Ñ s Âr ak³ @Îê. 6÷ õ k³ é³¶« Äî A ,

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(101) ê æ2 n- o «Ë ¡¤Q îw« ÀÉk k¿³ÑÓÑ ¬g õ k³ «d!Q é³¶s Ägá ê «d! õ Ä|s Î \H« DG.. [ ÷ á õg2 Éz/Ñw@î-à Ñw@ Qu,¬íè é³g T ÆÑ g ¤}æÉk, «Ñ Ý Ã?n.. ÷ô {S xi, xj φi. : liquid mole fraction of component i and j : fugacity coefficient of component i. R Tci, Tcj. : gas constant : critical temperature of component i and j. Tr Pci, Pcj. : reduced temperature : critical pressure of component i and j. ZRAm ZRAi. : rackett compressibility factor of mixture : rackett compressibility factor of component i. Vci, Vcj. : critical volume of component i and j. Vm Vi*, Vj*. 59. : molar volume of mixture : parameters for HBT correlations of component i and j. : parameters for HBT correlations of mixture Vm* ωSRKi, ωSRKj : parameters for HBT correlations of component i and j ωSRKm kij. : parameters for HBT correlations of mixture : binary interaction parameter. φ α. : the volume fraction of the dispersed phase : characteristic factor (=1.5). σ σm. : the conductivity of the macroemulsion system : the conductivity of the continuous medium. σ/σm. : ratio of the conductivity of the macroemulsion system against the conductivity of the continuous medium. S+S 1. Yoshida, H., Sone, M., Mizushima, A., Abe, K., Tao, X. T., Ichihara, S. and Miyata, S., “Electroplating of Nanostructured Nickel in Emulsion of Supercritical Carbon Dioxide in Electrolyte Solution,” Chemistry Letters, 1086-1089(2002). 2. Yoshida, H., Sone, M., Mizushima, A., Yan, H., Wakabayashi, H., Abe, K., Tao, X. T., Ichihara, S. and Miyata, S., “Application of Emulsion of Dense Carbon Dioxide in Electroplating Solution with Non-ionic Surfactants for Nickel Electroplating,” Surface of Coating Technology, 173, 285-292(2003). 3. Park, J. Y., Lee, C. H., Lee, Y. W. and Lim, J. S., “Electroplating of Ni on Cu in Ni-plating Solution/scCO2 Emulsion,” Proceedings of 1st International Symposium on Supercritical Fluid Technology for Energy and Environment Applications, 328-331 (2002). 4. Park, J. Y., Lee, C. H., Lee, Y. W. and Lim, J. S., “The Effective Electroplating using Macroemulsion in Supercritical CO2”, Proceedings of 2nd International Symposium on Supercritical Fluid Technology for Energy and Environment Applications, 76-79(2003). 5. Clauss, M., “Dielectric Properties of Emulsions and Related Systems,” vol.1, first ed., Decker, New York(1983). 6. Lee, H. R., “Surface Engineering,” Hyung Seul Publishing, 95102(1999). 7. Reid, R. C., Prausnitz, J. M. and Poling, B. E., “The Properties of Gases and Liquids,” fourth edition, McGraw-Hill Company, 89(1986). 8. Hankinson, R. W. and Thomson, G. H., “A New Correlation for Saturated Densities of Liguids and their Mixtures,” AICHE J., 25(4), 653-663(1979). 9. Liu, Z. T. and Erkey, C., “Water in Carbon Dioxide Microemulsions with Fluorinated Analogues of AOT,” Langmuir, 17(2), 274-277(2000). 10. Eastoe, J., Nave, S., Downer, A., Paul, A., Rankin, A., Tribe, K. and Penfold, J., “Adsorption of Ionic Surfactants at the Air-Solution Interface,” Langmuir, 16(10), 4511-4518(2000). 11. Kim, H. W., Jin, Y. W., Park, K. H., Kim, H. D., Yoon, B. H. and Wai, C. M., “Metal Nanoparticle Synthesis and its Catalytic Organic Reactions in Water-in-CO2 Microemulsion using Fluorinated AOT,” Proceedings of 1st International Symposium on Supercritical Fluid Technology for Energy and Environment Applications, 383-388(2002).. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

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