TRIN KHAI NG DNG CNG NGH BC X KH TRNG VT LIU POLYPROPYLENE DNG TRONG Y T

ng c Nhn1 , Trn Thanh Sn2 , V Vn Thun1 , H Minh c1 , Nguyn nh Dng1 , Nguyn Quang Long1 , Trn Minh Qunh

1) 2)

Vin Khoa hc v k thut ht nhn Vin Khoa hc k thut nhit i, Trung tm KHTN&CNQG

M U
Vt liu polymer ngy cng c s dng rng ri trong nhiu lnh vc ca nn kinh t quc dn. Cc lao polymer c dng ph bin lm vt liu bao b ng gi, ng dn nc v.v trong i sng dn dng. Polymer thng c dn in km nn chng c dng lm vt liu cch in trong nhiu ngnh k thut. My chc nm tr li y AIDS, vim gan B( Hepatilis) ang tr thnh nn dch nhiu nc trn th gii lm cho chng ta phi c nhng gii php khoa hc phng bnh. Bm kim tim mt ln lm bng vt liu polymer l mt v d in hnh ca v d ny. Dng c y t cn phi c cc tiu chun v bn c- l- ha nht nh, hn na n cn phah sch tuyt i. Chng phi c thanh trng ht vi khun, vi rt, nm cng nh cc vi sinh vt gy bnh lun c mt trn b mt dng c. Tiu chun v sinh thanh trng thng phi t 1/106, tc l xc sut cn nhim tc nhn gy bnh ca dng c y t kh trng l 10-6. C ba phng php kh trng chnh, l hp nhit (120-1300C), dng tc nhn ha hc( Ethylen Oxide, EtO) v dng nng lng ca bc x ion ha hay cn gi l kh trng bc x ( radiation sterilization). i vi cc dng c y t bng cht do, phng php hp kh trng khng th dng c v vt liu khng bn nhit. Theo thng k ca cc chuyn gia kh trng dng c y t [1,2], hin ti 70% s dng c cht do dng tring y t c kh trng bng phng php ha hc s dng kh EtO, ch yu l cc nc ang pht trin. Ti cc nc pht trin cng ngh kh trng dng c y t bng EtO b cm s dng, v kh ny l tc nhn gy ung th. cc nc ny, t nhng nm 70 cng ngh kh trng bng EtO c thay th bng cng ngh kh trng bc x, l ngun ng v pht tia gama nh Co-60, Cs-137 hoc my gia tc chm in t( EB machine). Kh trng bc x c u im l khng gy nhim mi trng cng nh khng c nguy c gy ung th cho ngi s dng nh trng hp EtO. c bit l cng ngh kh trng bc x cho php kh trng dng c dng ng gi kn, do vy hon ton loi b kh nng ti nhim trc khi thnh sn phm cui cng. Nhc im ca cng ngh bc x l n d lm thay i cc tnh cht cl-ha ca vt liu, v d lm gim bn c hc hoc bin mu do nhng thay i ha hc c bn trong lng vt liu di tc dng ca bc x, gy cm gic khng sch cho dng c. V vy, vic tm cng thc loi vt liu polymer bn bc x l nhng nghin cu t m ca nhiu nh khoa hc trn th gii. Loi cng

thc ny l nhng b mt cng ngh c chuyn giao cho cc hng sn xut dngc c y t kh trng bc x. Ta c th bt gp nhiu hng sn xut v cho bn loi Polypropylene(PP), Polyvinylchloride(PVC) bn bc x trn th gii ca cc nc Anh, Php, c, Nam T, M , Nht Bn, Ga bn ca loi vt liu ny thng gp 3-4 ln loi PP hoc PVC thng thng. Vin khoa hc v k thut ht nhn nhn thc c tnh kinh t v ngha thc tin ca vn kh trng bc x nn ngh B Khoa hc Cng ngh v Mi trng u t tin hnh ti : Trin khai ng dng cng ngh bc x kh trng Polypropylene v c cht dng trong y t v sinh hc trong hai nm 19981999. Mc ch ca nghin cu l tm cng thc loi nha PP bn vi bcx gamma dng sn xut bm kim tim mt ln kh trng bng bc x gamma ngun Co-60 ca Vin KH&KTHN. Bo co ny trnh by kt qu nghin cu ca ti ny trong vng hai nm qua. Phn 1: TNG QUAN TI LIU Trong phn ny s trnh by cc vn sau y: 1.Nhng vn chung ca tng tc bc x ion ha vi vt liu polymer 2.S thay i cc tnh cht c-l-ha ca polymer di tc dng ca bc x ion ha 3.Phng php n nh cng thc polymer tng cng kh nng chu bc x ca n 1.Nhng vn chung ca tng tc bc x ion ha vi vt liu polymer: Khi c bc x ion ha tng tc vi cc phn t polymer (P) mt lot cc sn phm s cc nh in t dng b by etr cng nh dng solvat ha es, cation P+, phn t P trng thi kch thch P+, v radical P- s c to ra: P --- ~~ --> P+ + etr(es) P --- ~~ --> P* --> P + E (1) (2)

Nh vy, khi chiu x, trong polymer s hnh thnh cc tm c hot tnh cao (cc cation, phn t kch thch, cc radical) hay cn c gi l cc sn phm phn ly bc x, l nhng tc nhn trc tip gy nn nhng thay i ha hc trong lng n.

Bng chng v s c mt cc in t b by, etr , cng nh cc in t solvat ha, es, trong lng polymer c kim chng bng phng php chp ph cng hng t in t (EPR) mt s polymer khi chiu x chng nhit tht, v d 77 v 4,2K. Trong trng hp ny, s xut hin etr v es trong polymer chiu x cng nh trong cc matrix rn khc c c trng bi cc vch singlet rt p trong ph EPR v cc vch ph rng ca ph hp th quang c vng nh sng nhn thy v trong vng ph hng ngoi [3,4]. i lng c trng cho mc to cc loi in t ny l hiu sut to in t Ge ca bc x. Ge c tnh bng s in t to ra trong vt liu khi n hp th nng lng 100eV. i vi cc polyolefin, thc nghim cho thy i lng Ge ph thuc vo mc tinh th ha (Crystalinity) ca vt liu polymer v nhit chiu x. Mc tinh th ca polymer cng cao hoc nhit chiu x cng thp, gi tr Ge ca cc polyolefin cng ln. Nh vy c th thy phn tinh th ca polymer chnh l cc by bt gi cc loi in t hnh thnh trong vt liu khi n b chiu x. Mt cc in t to ra trong vt liu cng ln cng ng ngha vi cc cation to ra trong n ( phn ng 1). Cc cation to ra trong polimer chiu x c kh nng mt i do qu trnh ti hp vi cc in t dng b by, hoc trng thi solvat ha. Trong trng hp ny s to ra cc phn t polymer b kch thch. Mt khc cc cation ny c th chuyn in tch cho cc phn t thu nhn (acceptor) in tch, c bit l cc vng thm benzen hoc pyren m chng thng c mt trong cc vt liu vi vai tr ph gia. V d: pht hin thy c cation-radical pyren vi hiu sut cao, ti 1,8ion/100eV [5] trong polyethylene c cha pyren khi n b chiu x. Cation polymer cng c th mt i do qu trnh chuyn proton v to radical: ~CH2+~ + ~CH2~--> ~CH~ + ~CH3+~ (3) Khi hp th nng lng bc x, phn t polymer c th ch b kch thch ln ti mc nng lng cao hn m thi. Sn phm phn ly bc x trong trng hp ny l cc phn t polymer kch thch. Vic truyn nng lng bc x ny c th xy ra trong polymer l do mch phn t polymer tng i di v c cc phn t mch lp li trong n. C hai loi hnh truyn nng lng trong vt liu polymer

khi n nhn nng lng bc x. Th nht, nng lng c th truyn gia cc phn t trong cng mt phn t vt cht. Th hai l nng lng c th c truyn gia cc phn t polymer khc nhau. Trong trng hp th hai vic truyn nng lng c thc hin theo hai c ch: c ch cng hng trao i v c ch cng hng cm ng. Theo c ch th nht, lp v in t ca phn t cho nng lng chm ln lp v in t ca phn t nhn nng lng v nh vy qu trnh chuyn nng lng c thc hin thng qua qu trnh trao i in t gia phn t giao ng cng mt tn s phn t nhn nng lng. C ch th hai xy ra khi hai phn t giao ng cng tn s. Tt c cc sn phm phn ly bc x k trn cui cng cng s gp phn vo vic to ra polymer chiu x cc radical t do. C th thy ba nhm radical c to ra do qu trnh phn ly bc x, l macro radical, radical phn t thp v cc radical to ra t cc qu trnh chuyn ha cc phn t ph gia cng nh tp cht c mt trong polymer. Cc macro radical c hai loi, mt loi c to ra do s phn ly nguyn t cng nh nhm nhnh gia mch polymer. V d: ~CH 2CHCH2~. Mt loi khc to do qu trnh phn ly nguyn t hoc nhm nhnh cui mch polymer. V d: ~CH2CH2~. Mt trong cc nguyn nhn chnh to radical trong polymer chiu x l c s tng tc gia cc loi in t ro ra do phn ly ba x vi phn t polymer. Khi chiu x Polyvinylchloride (PVC) nhit thp cc tc gi [4,6] pht hin tn ti radical ~CH2CHCH2~. Nguyn nhn chnh l do qu trnh: ~CH2CHClCH2~ + e --> ~CH2CHCH2~ + ClTuy nhin, nhit phng ngoi radical trn cn pht hin thy c radical allyl v polyellyl ~CHClCH(CH=CH)nCHCl~, vi n>=1 2.Nhng bin i c-l-ha trong polymer di tc ng ca bc x 2.1Nhng bin i ha-l ca polymer di tc ng ca bc x Nh trnh by phn 1, cc sn phm s cp to ra trong polymer khi chu bc x l cc loi in t, cc cation, cc radical l nhng tc nhn trc tip gy nn nhng bin i ha hc th cp trong lng n. Cc qu trnh ha bc x

th cp vi s tham gia ca cc sn phm phn ly bc x vi cc phn t mi trng xung quanh n s xy ra tc th khi c qu trnh ion ha s cp. Cc qu trnh ny quyt nh s thay i cu trc ha hc ca vt liu chiu x v ko theo l cc bin i v tnh cht c l ca n. Khi b chiu x, trong polymer xy ra hai qu trnh bin i: bin i thun nghch v bin i khng thun nghch. Bin i thun nghch l qu trnh m cc thnh phn khng v to ra trong khi b chiu x c th chuyn ngc v dng ban u ca n. V d: phn t P* b kch thch n mc nng lng cha cao phn ly, chng c th bc x nng lng d ra mi trng chuyn v dng cn bng ban u. Nhng bin i khng thun nghch l cc phn ng ha hc gia cc sn phm phn ly bc x vi cc phn t, nguyn t mi trng. y l nhng bin i ha hc m bn cht l cc qu trnh chuyn ha cc sn phm phn ly bc x (cation, radical) c hot tnh cao trong vt liu b chiu x to ra cc sn phm mi bn vng. Ty thuc vo cc c tnh ring ca vt liu nh cu to ha hc, s sp xp mch cao phn t, c tnh ca qu trnh polymer ha, s c mt trong vt liu cc thnh phn phan t bc thp vi bn cht khc nhau v iu kin chiu x nh nhit , sut liu, thnh phn mi trng chiu x v.v m khi b chiu x, trong polymer s c cc hiu ng khng thun nghch sau:

Khu mch (crisslining): hnh thnh cc mch ngang gia

cc nt C-C hoc dng khc to mng cu trc khng gian ba chiu, khng tan trong cc dung mi hu c.

Gy mch (scission): cc lin kt ha tr trong mch chnh hoc Thay i mc no (change of unsturity) ca phn t: mt ni i v

nhnh b b gy. tr ny to ni i v tr khc hoc tng mt ni i. 2.1.a. Hin tng khu mch bc x ca polymer Thng thng khu mch v gy mch xy ra ng thi trong lng polymer khi n chu bc x, tuy nhin t l tc ca hai qu trnh ny c hc nhau v t

l ny ph thuc vo cu trc ha hc ca polymer, trng thi vt l ca chng v iu kin chiu x. Do vy, ta ch c th ni vt liu polymer ny tri khu mch v vt liu polymer khc tri gy mch m thi. C tc gi cho rng [7] nhng polymer m trong mch chnh mi nguyn t carbon c t nht mt lin kt vi nguyn t hydrogen, tc mch chnh ca n c cu trc ~CH2CHRCH2~ th hin tnh tri v khu mch, cn nhng polymer m mch chnh c cu trc ~CH2CHRCH2~, trong R v R khng phi l nguyn t hydrogen hoc halogen th hin tnh tri v gy mch. Tuy nhin cng c nhng ngoi l. Polypropylene (PP) alactic c t l hiu sut khu mch trn hiu sut gy mch bng 0.8, nhng PP isotactic t l trn l 1,4 [8]. C ngha l PP atacic tri gy mch, trong khi PP isotactic tri khu mc, trong khi c hai loi polymer ny u c cu trc mch tng t dng th nht, tri khu mch. Hn na quy tc trn cng ch ng trong trng hp chiu x polymer trong chn khng. Khi c mt khng kh, chnh xc hn l c mt oxy s c rt nhiu phn ng oxy ha ph khc xy ra, gy hin tng gy mch nh s trnh by mc hin tng oxy ha polymer khi chiu x sau ny. C ch phn ng khu mch c m t thng qua trng hp n gin, l khu mch chiu x ca polyethylene. Nh trnh by phn 1, di tc dng ca bc x ion ha, trong polyethylene s to ra cc radical nh mt sn phm s cp ca bc x. Cc radical ny s kt hp vi nhau to ra nhng mch lin kt ngang mi. l cc mch lin kt ngang trong cng mt phn t polyethylene: ~CH2CHCH2~ + ~CH2CHCH2~ --> ~CH2CHCH2~ (5) ~CH2CHCH2~ Loi lin kt ny c gi l lin kt hnh ch H Cng c th do c cch mch lin kt ngang m mch chnh b phn nhnh: CH2~ ~CH2CH2CH2CH2 CH2~ , lin kt ny gi l lin kt hnh ch Y (6)

Ngoi dng lin kt trong mt phn t polymer, cn c nhiu mch ngang c to ra do t qu ca cc li kt gia cc phn t polymer khc nhau. i lng c trng cho khu mch l hiu sut khu mch bc x. C hai khi nim v hiu sut khu mch bc x. Th nht, l i lng biu din bng s phn t cu trc (nt monomer) trong mch polymer c ni li vi nhau khi hp th nng lng bc x 100eV (i lng G). Th hai l i lng biu din bng s mch ngang c to ra trong polymer khi n hy th nng lng bc x 100 eV, i lng G(X). R rng rng G(X)=1/2G S hnh thnh cc mch nagng gia cc phn t polymer s lm tng trng lng trung bnh ca trng lng phn t (weight average molecular weight, Mw). mt liu chiu nht nh no , do c khu mch, m mt phn polymer khng tan c trong bt k loi dung mi hu c no, phn ny c gi l phn gel (gel fraction, g). Hin tng ny c gi l hin tng to gel bc x v liu ti thiu tp gel trong polymer gi l liu to gel. Ngc li, phn ha tan s=1-g gi l phn sol (sol fraction). Bng thc nghim ta c th xc nh c i lng G(X) cho tng loi polymer, da vo biu thc [9]: G(X) = 4.83.103/DgMw phn t polymer im to gel. T biu thc (7) d dng nhn thy, xc nh G(X) ta chiu x polymer vi cc liu khc nhau xc nh liu Dg ; ng thi xc nh phn b trng lng phn t polymer theo liu chiu xc nh Mw ri tnh G(X). Bng 1 trnh by gi tr G(X) ca mt s polymer thng dng. Bng 1 Ga tr hiu sut khu mch , G(X) ca mt s polymer thng dng. Polymer Polymethylene t trng thp, LDPE Polymethylene t trng cao, HDPE Polymethylene isolactic, PP iso lactic Polymethylene atatic, PP atatic G(X), eV 0,8-1,25 0,7-1,1 0,3-1,25 0,3-0,5 mch/100 Theo ti liu [10] [10] [11] [11] (7) Trong : Dg l liu to gel v Mw l trng lng trung bnh ca trng lng

Copolymer ethylene-propylne Polyvinychloride(PVC) Cao su thin nhin Nynol T bng 1 ta thy , i vi cng ,mt

1,1 0,3 1,3-1,5 0,7-0,9 loi polymer, gi tr

[12] [13] [14] [15] G(X) thay i trong

khong rng. iu ny c gii thch l th nghim xc nh i lng G(X) c tin hnh vi nhiu loi mu c mc tinh th khc nhau. Khu mch xy ra ch yu vng v nh hnh ca polymer. Ti cc vng ny cc i phn t ca polymer sp xp chng cho ln nhau lm cho qu trnh to mch ngang thun li hn. Ngoi ra, ti cc ti cc vng ny mc ng ca cc radical cng ln hn so vi chng vng tinh th, s sp xp cc i phn t c trnh t nht nh. Tuy nhin, ti cc vng i phn t vn c s chuyn dch ha tr t do t trong lng cc lamell ra vng bin, do vy cc lin kt mch ngang trong cng mt phn t polymer s xy ra ch yu y. Do c khu mch m tnh cht c-l ca vt liu polymer tng ln r rt. V d: polyethylene chiu x n gel khong 50%, tc l khong 50% trng lng polymer khng tan c trong dung mi lm tng cch in ca n ln gp 3-4 ln so vi nha khng c bin tnh, ng thi mc ko di ti thi im t ca n cng c tng ln i cht. Tuy nhin nu gel cao hn na, 80-90% chng hn, th mc ko di ti im t s gim i, vt liu tr nn cng v rn hn. Bin tnh vt liu polyethylene bng cng ngh bc x c trnh by tng i k trong nhiu bo co tng quan, v d trong [16]. 2.1.b. Gy mch bc x trong polymer Di tc dng ca bc x, cng vi qu trnh khu mch, trong polymer ng thi xy ra qu trnh gy mch. Hin tng ny biu hin qua s gim trng lng phn t ca i phn t polymer, hon ton khc qu trnh depolymer ha, tc l qu trnh to ra cc monomer c cu trc mch bc bn ~CH2CRRCH2~ th hin tnh tri gy mch bc x. Khi b chiu x, cc radical to ra t loi phn t polymer tri gy mch bc x t c kh nng ti hp vi nhau v hiu ng khng gian. Hn na, do c nguyn t cacbon bc bn nn vic di chuyn ha tr dc

theo mch cng khng th thc hin c [17]. Chnh v cc l do nn cc radical ny ch yu ch c kh nng t phn hy hoc tc dng vi cc radical c trng lng phn t thp. C ch gy mch bc x ca polyisobuthylene (tng t nh polypropylene) l trong chng to ra cc radical v tr cui mch [4]: Tc cng nh kh nng xy ra cc phn ng trn tng theo nhit . Hiu sut phn ng gy mch bc x, G(S) c xc nh bng cng thc [9]: G(S) = 9,65.103 (1/Mn - 1/Mn,0)/D (10) Trong Mn v Mn,0 l trng lng phn t trung bnh ca polymer sau v trc hi chiu x, D l liu chiu x tnh bng Mrad (1 Mrad = 10Gy). Nh vy, s ph thuc gia i lng (1/Mn - 1/Mn,0) v liu chiu l mt ng thng c h s gc bng G(S).D/9,65.103. Do vy, bng thc nghim ta c th xc nh c gi tr G(S) ca polymer khi chiu n cc liu khc nhau bng cch xc nh s ph thuc gia trng lng phn t trung bnh ca polymer vi liu chiu [9]. Trong bng 2 l gi tr G(S) ca mt s loi polymer. Bng 2. Gi tr G(S) ca mt s loi polymer thng dng Polymer Polypropylene atactic Polymerpropylene isotactic Copolymer ethylene-propylene Polyethylene Cao su thin nhin Nylon G(S), (s mch gy / Ngun ti liu 100eV) 0,3-1,8 0,3-0,6 0,33 0,4-0,5 0,13 2,4 [11] [11] [12] [18] [19] [15]

2.1.c.To kh v thay i lin kt ha tr trong polymer di tc ng ca bc x Di tc dng ca bc x, trong polymer ngoi cc phn ng khu mc v gy mch, qu trnh to cc loi kh cng nh thay i lin kt ha tr, t mc no chuyn sang ni i cng xy ra kh mch. i vi cc loi olefin, khi b chiu x,

kh hydrogen c to ra vi hiu sut ln nht. V d G(H3) ca polyethylene di tc dng bc x gamma hoc chm electron l 3,7. Ngoi kh hydrogen, nhiu loi kh khc cng c hnh thnh, v d CH4, CO2, CO.v. .. khi chiu x cc loi polymer khc nhau. Bng 3 l gi tr hiu sut to kh t cc polymer chiu x khc nhau. Bng 3. Hiu sut to mt s loi kh di tc dng ca bc x gamma, hoc chm tia in t nhit phng v trong chn khng Polymer Polyethylene Polypropylene isotactic Polypropylene atactic Polyvinylchloride, PVC Polyvinylacetate Sn phm kh H2 CH4 H2 CH4 H2 CH4 HCl H2 CH4 H2 CH4 CO Hiu sut to kh 3,7 <0,02 2,87 0,07 2,34 0,10 7,5 0,15 0,0002 0,64 0,34 0,18 Ti liu [20] [20] [20] [20] [20] [21] [22] [22] [23] [23] [23]

CO4 0,06 [23] Qu trnh thot kh do bc x polymer l mt trong cc nguyn nhn to thm cc mch ni i trong phn t vt liu ny. S hnh thnh thm cc ni i l mt trong nhng nguyn nhn lm bin i mu ca polymer chiu x. 2.1.d. Oxy ha bc x v oxy ha sau bc x ca vt liu polymer i b phn cc polymer khi chiu x trong mi trng c oxy u b oxy ha. Phn ng oxy ha bc x xy ra khi c mt oxy khng nhng trong mi trng xung quanh vt liu (khng kh) m n cng xy ra i vi oxy ha tan trong lng vt liu. u tin oxy ha xy ra gia cc sn phm phn ly bc x vi oxy tan trong lng polymer, sau khi lng kh ny s dng ht, m bc x vn duy tr s c s khuych tn oxy mi trng tip tc duy tr qu trnh trn. Hn

na, sau khi chiu x mt thi gian tng i di qu trnh oxy ha vn cn tip tc, l do cc sn phm phn ly bc x i khi c thi gian sng kh lu. Oxy ha l hin tng lm gim cc tnh cht tt, cn c ca vt liu v do rt cn hn ch qu trnh ny khi chiu x vt liu polymer . C ch qu trnh oxy ha bc x c m t tm tt nh sau: P P, radical polymer P + O2 PO2, peroxide radical (11) (12)

Peroxide radical s chuyn thnh hydroperoxide radical POOH, t to ra radical OH v PO. Chnh cc radical PO s t phn hy to nhm carbonyl v radical P, phn ng oxy ha bc x trong polymer l phn ng dy chuyn. S hnh thnh nhm carbonyl th hin rt r s xut hin vch ph 1716 cm -1 trong ph hng ngoi ca cc polymer olefin. Tc oxy ha bc x ph thuc rt nhiu vo xut liu. iu ny chng t khuych tn l qu trnh quyt nh tc phn ng oxy ha. 2.2. S thay i tnh cht c-l ca vt liu chiu x. Khi chiu x liu cao, modul n hi cng nh bin dng ca vt liu s tng ln, lm cho tui th ca n gim i. Tt nhin, mc thay i( theo gi tr tuyt i) cc i lng ny ph thuc vo loi vt liu c th. Tui th ca vt liu gim, mt mt do qu trnh gy mch chnh, mt khc do qu trnh oxy ha bc x trong vt liu. cc loi polymer c cu trc bn kt tinh th khi b chiu x liu cao (ln hn 1 Mgy), phn tinh th ca vt liu s b ph hy mt phn. Cng chnh v vy m kh nng chu ti ca vt liu gim r rt v n tr nn rn. Trong cc loi polymer tri khu mch, khi mt khu mch tng i cao( khong 50%), th cc mch ngang ny cn tr qu trnh ti tinh th ha trong polymer v n lm cho vt liu c trng thi nh cao su trong gin nhit ca n. Cng chnh v c hin tng ny m vt liu chiu x c mt tnh cht rt c bit l c kh nng nh. Hin tng nh ca vt liu chiu x khu mch th hin ch khi gia nhit n gn nhit nng chy ca vt liu ta d dng bin i kch thc cng nh hnh dng ca sn phm v lm ngui t ngt, n gi nguyn trng thi mi, nh mt dy cao su c ko cng v gi bng ngoi lc. Nu gia nhit tip, tc l loi b ngoi lc, th sn phm s quay li nguyn dng ban u ca n. Hiu ng ny c ng dng rng ri trong cng ngh bin tnh vt liu, c bit l polymethylene, to ra cc ng ni cch in, chng thm, chng m ti nhiu nc trn thi gii.

Tuy nhin trong thc t, hu ht cc loi vt liu polymer khi b chiu x u b suy gim cc tnh cht c-l. iu cn thit l phi n nh chng chng c kh nng bn vi bc x nhng liu chiu khc nhau. 3. Cng thc n nh polymer bn bc x. Nguyn tc n nh polymer lm cho vt liu bn di tc ng ca bc x l cn c thm cc ph gia trong cng thc ca n. Cc ph gia ny phi c kh nng hp th nng lng bc x mt cch thun nghch. Mt loi ph gia khc rt cn thit l cc cht chng oxy ha. Cc cht ny c nhim v tiu th lng oxy ha tan cng nh lng oxy khuych tn t mi trng ngoi. Da trn nguyn tc ny, cho n nay tt c cc cng thc polymer dng trong i sng u phi c cc cht c chc nng hp th tia cc tm v cc cht antioxidant. Ngoi nguyn tc cho thm ph gia, ngi tac cn c th n nh polymer bng cch tng phn v nh hnh ca vt liu. Phn v nh hnh cu vt liu s thay i khi to cc copolymer. Copolymer ethylene(6%)- propylene c tnh chu bc x hn hn polypropylene. Cng trn nguyn tc ny, ngi ta ngi ta trn hai loi polymer c tnh tri khu mch hoc gy mch khc nhau cng c th to c vt liu mi bn bc x. Tuy nhin, phi phi tm c cc loi polymer c tnh tng hp vi nhau th mi c th gia cng to c sn phm. Polypropylene trn vi mt s loi cao su nhn to vi t l nht nh cng cho loi cng thc polypropylene bn vi bc x liu chiu kh cao (50-70 kGy). Thc t cng cho thy, polymer c trng lng phn t cao bn vi bc x hn cc polymer trng lng phn t thp. PHN II. PHNG PHP THC NGHIM i tng ca nghin cu ny l nha Polypropylene ang dng sn xut bm kim tim mt ln v bn ti Ha Ni. Nha PP c cu trc bn tinh th nh trnh by trn hnh 1. 1.Thnh phn mt s loi PP dng sn xut bm kim tim mt ln bn trn th trng H Ni Trn th trng H Ni, ti cc hiu thuc u c bn bm kim tim mt ln bng cht do kh trng, ch yu bng EtO. Cc sn phm ny c sn xut ch yu Hn Quc. C mt s loi loi bm kim tim kh trng bng bc x nhp t Php v Trung Quc. kho st thnh phn loi nha ca bm tim ny, phng php quang ph k TF IR (Trans Fourier InfraRed Spectrometry), phn tch nhit (TGA) v nhit vi sai(DSA) c p dng phn tch. My phn tch TF IR cng nh TGA u ca hng Shimadzu, Nht Bn v chng c vn hnh ti Vin Khoa hc hnh s, B ni v v ti phng th nghim cc phng php nhit, Vin Ha hc, TTKHKT&CN QG. 2. To mu vt liu nghin cu Trong nghin cu ny cc tc gi tp trung vo hai hng to cng thc vt liu bn bc x. Hng th nht l chn copolymer ethylene (2%)- propylene, c

ch s dng chy (MFI) bng 1( MFI l lng nha tnh bng gam b n ra khi thit b n nhit 1800C trong vng 10 pht v lc nn l 2,1 Kg). Trong cng thc ny ngoi nha ch cn trn thm 0,2 phr Stearate Calcium, 0,1 phr antioxidant nhm phosphorus. Theo hng ny mt cng thc khc ngoi cht tr gia cng v antioxidant s cp Alkanox 240, hng Great Lake Chem. Corp, cn trn thm 0.1 phr Amine c cu trc cng knh( hindered amine) l Tinuvin 662, hng Ciba Geigy lm cht antioxidant th cp, 0.2 phr cht lm trong l Benzoic Acid hoc Benzeoiate Sodium tinh khit ca hng Great Lake Chem. Corp Hng th hai l can thip vo trng thi hnh thi ca nha. Cc tc gi trn PP vi PE vi nhng t l khc nhau. Hn hp PP v PE c trn trong bung gia nhit ca thit b n nha vi ch gia nhit tng dn t 180 n 195oC cui u ra l khun p thy lc to ra tm nha c kch thc 100x 100 x 2(mm). Hnh 2 l tp hp 250 mu dng blend ny. 3. Nghin cu kh nng chu bc x ca cc loi vt liu PP. Bm tim ca Hn Quc mua ti hiu thuc, gi nguyn trang thi ong gi kn em chiu x trn ngun Co60 cu Trung tm chiu x, Vin khoa hc k thut ht nhn. Liu chiu l 10, 20, 30 kGy vi sut liu ln nht, khng qu 1.0 kGy/h( mu chiu t st bng ngun). Liu chiu x c xc nh bng cc dosimeter Perspex, hng Harwell, Anh quc. Sai s ca php xc nh liu chiu trong khong 6%. Cc mu t ch theo cng thc k trn c ng gi kn, thm ch c mu c thi kh nit mt cch cn thn sau hn li v em i chiu x. C mt lot mu chiu x trong iu kin h, nhm tm hiu mc nh hng ca oxy n qu trnh gy mch ca cng thc. Sau chiu x mu c phn tch v bn c l, l cng ko di ti im t, sc chu un cong, chp li cc ph TF IR, TGA v o h s vng ( Yellownes, YI). 4. Xc nh gi tr phn trm gin di ti im t ( % Elongation at break) % gin di ti im t ( E, %) ca vt liu c xc nh trn thit b chuyn dng ZMGJ ca hng Toyoseiki, Nht bn. Quy trnh xc nh c tnh ny c thit lp ti Tng cc tiu chun cht lng o lng Vit Nam. 5. Xc nh trng lng phn t trung bnh ca polymer trc v sau chiu x Mc ch ca th nghim ny l xc nh hiu xut gy mch ca mt s lao PP dng sn xut bm tim mt ln khi chu chiu x vi liu kh trng. Trng lnghj phn t trung bnh ca polymer c xc nh bng thc nghim ca php o nht thc t( intrinsic viscosity, [] [24] ca polymer vi trng lng phn t biu din bng biu thc bn thc nghim sau [25]: []=1,0. 10-2.M0.8 (dm3g-1) [13]

Nha PP trc v sau chiu x c ha tan vo dung mi nhit 1350C trn thit b o nht chuyn dng ca Anh quc. Trn c s mi tng

quan gia i lng (1/MD-1/M0) v liu chiu ta tnh c G(S), theo cng thc (10). Gi tr ca G(S) cho thy mc gy mch ca PP trong cc iu kin chiu x nht nh. 6. Xc nh ch s vng ca vt liu (ch s chuyn mu: yellowness index, YI) Ch s vng biu th s bin mu ca vt liu( t mu trng trong sang mu vng) do c nhng bin i v cu trc hoc thnh phn ha hc ca vt liu. i mu trong chiu x c th do xut hin nhng ni i mi trong phn t polymer, hoc do phn hy cc thnh phn phi trn khc c mt trong vt liu. Ch s ny c xc nh bi t s gia mt quang, thng qua i lng absorbance A, ca tm PP chiu x nhng liu chiu x nhng liu chiu khc nhau, A D c dy 1mm v mt quang ca tm PP i chng ( khng chiu x), A0, c di tng t o ti cc bc song 270 nm. YI= AD/A0 (14) Mt quang biu din qua i lng Absorbance (A) ca cc tm nha mi bng, c di chun l 1mm c o trn thit b Densitometer CS-9001PC hang Shimadzu, Nht Bn. Hnh 3 l ph hp th nh sang t ngoi ca PP chiu x vi cc liu chiu khc nhau, Absorbance cc i ca vt liu nhn thy 270 nm. Trong khi ph hp th t ngoi ca mu i chng khng c cc i ny. 7 Th nghim tnh tng hp gia PP v PE Hai loi PP v LDPE th nghim c trn vi cc t l khc nhau trn thit b HAAKE( Gemany). Thit b ny cn cho php xc nh c ch gia nhit cho tng loi polymer khi gia cng ch bin n. Gn thit b ny vi thit b p thy lc ta c th ch to c cc tm vt liu c dy chun trong cc nghin cu. Hnh 4 l gin phi trn hai loi nha trn. Trn hnh 4 trc tung bn tri l i lng moment xon ca mu to c, trc tung bn phi l nhit . S thay i moment xon c trng cho s hnh thnh nhng sn phm mi to ra do nhng phn ng, nu chng xy ra, khi phi trn hai loi nha vi nhau. T hnh 3 ta thy, hai laoaij nha PP v PE chn c tng hp tt vi nhau. Khi trn gia hai laoij nha ny khng c phn ng no xy ra, m ch l s ha trn c hc. V bn cht, hn hp ny ch mang tnh phi trn c hc vi nhau, do tnh hp th nng lng bc x ca PE vn m bo tt. PHN III. KT QU V THO LUN 1 . Thnh phn v cu trc ca mt s loi vt liu polypropylene. Hnh 5-7 l ph TF IR ca ba loi PP dung sn xut bm tim mt ln ly t ba hng Chun jee, Chun sol, v Vinahook, lin doanh Vit Hn, Thanh Tr, T Lim, H Ty. Ph hp th cho thy vt liu sn xut bm tim ca ba hng ch l nha PP. Cc nh hp th nh sng hng ngoi u rt c trng cho nhm CH3

thuc mch nhnh ca vt liu. Hnh 8 l ph TF IR ca blend Polyethylene( PE) vi polypropylene (PP) t ch to vi t l PE l 30 phr ( part per hundred of resin , phn trm nha chnh). Ph IR them mt nh bc sng 625 cm-1 , c trng cho nhm CH2 ca mch PE. Cc phn tch nhit (TGA) cho thy, vt liu PP ca ba hng trn rt khc nhau v thnh phn nha ch. Hnh 9-11 l gin TGA i vi ba mu PP ca ba hng trn. T 3 gin 9-11 ta nhn thy, lng mt trng lng ca ba loi nha khc nhau, tc phn nha ch ca ba loi nha ny khng nh nhau. Thnh phn nha ch trong vt liu PP ca 3 hng ln lt l 94%, 98%, 93%, phn cht n tng ng l 6%, 2%, 7%. Nhit bt u bay hi ca 3 vt liu cng khc nhau, PP ca hng Chun jee bt u bc hi 218 0C v kt thc 3340C , hng Chu sol tng ng l 3340C v 4160C, hng Vinahook l 2390C v 3420C. Nh vy c th thy rng hng Chun hng Chun jee s dng loi nha PP c trng lng phn tuer thp hn so vi vt liu ca Chun sol v Vinahook. Loi nha PP ca Chun sol c trng lng phn t cao nht. Theo Yoshii [26], PP c trng lng phn t cao, t l phn v nh hnh ln thng bn hn vi bc x so vi loi c trng lng phn t thp, t l phn v nh hnh nh. Hnh 12 l gin TGA ca blend PE/ PP, 30 phr PE, mt trong cc i tng nghin cu ca nghin cu ny. Hai loi PE v PP chn cho nghin cu ny c tnh tng hp tt( hnh 4). 2 Kh nng bn bc x ca mt s loi vt liu polypropylene Hnh 13-15 l gin TGA ca ba loi vt liu PP ly t bm tim ca ba hng sn xut nh trnh by phn 1 v chng c chiu x vi liu chiu 30 hoc 50 kGy. Hnh 16 l gin TGA ca blend PE /PP, 30 phr PE cng c chiu x vi liu 30 kGy. Nhn thy vi liu chiu ny trong ba loi nha ca ba hng sn xut mt phn mch chnh ca PP b gy v hnh thnh mch c trng lng phn t thp. iu ny th hin nhit bt u bc hi gim tt c ba loi nha khi chng b chiu x. Nhit bt u bc hi ca hng Chun jee gim t 218 xung 2150C sau khi chiu x vi liu 30kGy v ca hng Vinahook t 239 xung 2040C. Tuy nhin, song song vi qu trnh gy mch cng thy mt phn polymer c khu mch lm tng trng lng phn t do vy do vy nhit bc hi cng tng mt s loi PP nghin cu. Tr PP ca hng Chun sol l khng thy c khu mch, v nhit kt thc bc hi gim t 417 xung 4020 C, hai loi nha PP ca Chun jee v Vinahook u c nhit kt thc bc hi cao hn so vi i chng (hnh 13 v hnh 15). Ngc li, loi blend t

ch to khng thy c hin tng gy mch, v nhit bt u bc hi ca vt liu chiu x (hnh 16) khng thay i so vi mu i chng( hnh 12) Bng 4 trnh by bn c l ca cc vt liu PP nghin cu trc v sau khi chiu x liu 30 kGy. Trong bng ny ngoi s liu ca ba loi vt liu sn xut bm tim ca ba hng trn cn c kt qu ca mu blend PP-PE cng nh cc loi PP t phi trn. bn c l y c biu din qua i lng % gin di tng i( ER, %) v tnh theo cng thc ER,%= EB,ir/EB,0.100 (15) Trong EB,ir l gin di ti im t ca mu sau khi chiu x vi liu nht nh EB,0 l gin di tai im t ca mu i chng Bng 4. Ga tr % ER ca cc mu PP chiu x liu 30 kGy No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Mu vt liu PP,hng Chun jee PP, hng Chun sol PP, hng Vinahook Blend PPPE(00phr PE) Blend PPPE(01phr PE) Blend PPPE(02phr PE) Blend PPPE(03phr PE) Blend PPPE(04phr PE) Blend PPPE(06phr PE) Blend PPPE(15phr PE) Blend PPPE(20phr PE) Blend PPPE(30phr PE) Blend PPPE(100phr PE) PP + Alkanox 240+ St Ca PP + Alkanox 240+ St Ca + Tv622+ Ba ER, % 85 73 82 85 93 96 97 97 98 96 99 99 100 0 95

Nhn chung, sau khi chiu x liu kh trng ( 25-30 kGy) cc loi PP dng sn xut bm kim tim u gi c tnh bn c l ca n, tr nha ca hng Chun sol c gim cht t. Tuy nhin cc cng thc to t PP n cht vi mt s ph gia cn n gin v chng loi ( antioxidant, cht ph tr gia cng nh Stearate Calcium, cng thc 14) khi b chiu x n 25 kGy tr nn rt gin,

bn c l ca chng khng cn na. Kt qu th nghim cho thy, cc cng thc PP c sn trn th trng khi b chiu x u b bin mu, trong khi cc cng thc n cht dng cng thc 14-15 hu nh vn gi nguyn c mu trng, trong. Nh vy bn cht cc antioxidant c nh hng rt ln n qu trnh to gy mch hoc to ni i bc x trong cc vt liu c sn trn th trng. Bng 5 trnh by kt qu o YI (cng thc 14) ca cc cng thc PP nghin cu. Bng 5. Gi tr Yellow Index (YI) ca cc cng thc PP nghin cu No Cng thc vt liu YI cc liu chiu 10 kGy I 1 2 3 4 5 6 7 8 9 10 11 12 13 14 2 Chun jee Chun sol VINAHOOK Blend PPPE (00phr PE) Blend PPPE (01phr PE) Blend PPPE (02phr PE) Blend PPPE (03phr PE) Blend PPPE (04phr PE) Blend PPPE (06phr PE) Blend PPPE (15phr PE) Blend PPPE (20phr PE) Blend PPPE (30phr PE) Blend PPPE (100phr PE) PP + Alkanox 240 + St Ca1 3 1.23 1.26 1.20 1.26 1.20 1.22 1,20 1.22 1.16 1.13 1.10 1.06 1.00 1.00 30 kGy 4 1.45 1.41 1.35 1.38 1.31 1.35 1.35 1.36 1.30 1.21 1.20 1.10 1.00 1.00

15

PP + Alkanox + St Ca + Tv 622 1.00 + BA 3. Oxy ha bc x ca PP

1.00

Hnh 17 v 18 l ph TF IR ca mu to vt liu PP SJ 150 dng sn xut bm kim tim ca hng VINAHOOK, trc v sau khi chiu x liu 30 kGy trong mi trng Nit (hnh 17) v khng kh (hnh 18). Hnh 18 cho thy, do c khng kh (oxy) nn ph IR ca vt liu PP chiu x xut hin vch ph 1716 cm-1, c trng cho nhm cacbonyl (mc d, im 2 phn tng quan ti liu). Trong khi , khi chiu x vt liu PP trong mi trng nit th vch ny khng c. Trong iu kin c khng kh, mc d sut liu nh, khng qu 0.3 kGy /h tc thi gian chu bc x ca vt liu kh lu ( gn 10h t liu chiu 25-30 kGy ) nhng vch ph c trng cho nhm cacbonyl cng khng ln. Mc hnh thnh nhm cacbonyl do oxy ha PP trong chiu x c c trng bi i lng Carbonyl Ind, CI. l t s chiu cao hai pic: pic 1716 cm-1 v 841.1 cm-1. Trong trng hp ny CI ch trong khong 0.1. iu ny c gii thch l do vt liu em nghin cu l loi c thnh phn chu bc x t nhin, tc l trong thnh phn ca n c sn cht ph gia nh cht antioxidant, cht hp ph UV v.v... nn kh nng oxy ha ca n liu chiu x 30 kGy b hn ch rt nhiu. Tuy nhin, loi antioxidant dng trong thnh phn ca n cha thch hp nn vn gy i mu. Kt qu phn tch phn b trng lng phn t theo liu chiu (cng thc 13) xc nh c G(s) ca PP SJ 150 ca hng VINAHOOK trong mi trng khng kh l 0.51 ln gp 10 ln so vi G(s) ca vt liu trong mi trng nit, G(s) = 0.05 [27]. PHN IV. KT LUN

1. Cc tnh cht c l ca vt liu PP vi cng thc n gin, v d cng

thc 14, b gim nhiu ( vt liu khng c kh nng gin, gi tr % ER =0) vt liu tr ln gin, d v khi b chiu x, thm ch vi liu 2030kGy. 2. hn ch yu im trn cn c cc cng thc c bit. Cc antioxidant c bn cht l phenolic u gy i mu (trng sang vng) khi chng b chiu x. 3. Blend PP-PE vi t l 30 phr PE vi antioxidant l Alkanox 240 v Tv 622 l loi vt liu bn bc x c th dng lm vt liu sn xut dng c y dc kh trng bng bc x.

4. Chu trnh cng ngh to sn phm bm tim t Blend PP/PE v kh

trng bng chiu x gamma tin hnh nh sau: trn 30 phr nha PE vi PP trong bung gia nhit 180, 185 v 1900 C trong 10 pht (hnh 3), ri n hn hp vo khun, lm ngui nhanh (< 20 giy). Sn phm ny c phn v nh hnh ln, bn bc x vi liu chiu kh trng 25-30 kGy. TI LIU THAM KHO