TP CH KHOA HC V CNG NGH, I HC NNG - S 1(36).

2010

NGHIN CU CI THIN TNH NNG CA VT LIU COMPOSITE SI AY/ NHA POLYPROPYLENE BNG PHNG PHP BIN TNH NHA NN
INVESTIGATION ON IMPROVING THE PERFORMANCES OF JUTE/POLYPROPYLENE COMPOSITE BY MATRIX MODIFICATION on Th Thu Loan

Trng i hc Bch khoa, i hc Nng

TM TT Cc polymer gia cng si t nhin c nhng tnh cht c hc v khng nc khc nhau ph thuc vo bn cht b mt tip xc gia nha v si. Trong nghin cu ny, nh hng ca cc tc nhn tng hp copolymer ghp ca polypropylene v anhydride maleic i (MAHgPP) n tnh cht ca composite nn nha polypropylene gia cng si ay c kho st. Kt qu cho thy khi thm 2% khi lng Exxelor (Ex) vo nha nn polypropylene th bn kt dnh ti b mt tip xc ci thin ng k do vy lm tng bn ko trt, bn ko, bn va p v khng nc, tuy nhin khng nh hng n module ko ca mu composite. S thay i bn kt dnh ti b mt tip xc v hnh thi b mt ph hy c nh gi bng cch s dng co mposite si n qua cc phng php phn tch hin i gm th bn ko trt composite si n v knh hin vi lc nguyn t (AFM). ABSTRACT Natural bre reinforced polymer matrices can exhibit very di erent mechanical performances and water resistance depending on interphase properties between fibre and matrix polymers. In this study, investigations of the effects of compatibilisers based on maleic anhydride grafted polypropylene copolymers (MAHgPP) on the properties bre jute of reinforced polypropylene composites have been considered. The addition of 2 wt% Exxelor (Ex) compatibilisers to polypropylene matrix (PP) can signicantly improve the adhesion strength with jute bre and in turn the mechanical properties, including interfacial adhesion strength of jute/PP micro-composite; tensil strength and impact strength of jute/PP macro-composite; and water resistance of jute/PP macro-composite samples. However, strength module of macro-composite samples is not changed by using 2 wt% Ex. The changes of interfacial adhesion strength and fracture surfaces were characterized using jute single fibre model composites (micro-composite). The modern investigated methods, including single fibre pull out test and atomic force microscopy (AFM) were used to investigate interfaces and topography, respectively.

1. t vn Si t nhin c dng lm composite cch y 3000 nm Ai Cp c i. Vt liu composite nhn to u tin ny c lm bng cch trn rm v t st lm nh. Tuy nhin s quan tm nghin cu v s dng si t nhin gia cng cho vt liu composite ch mi vi thp k qua. Nhng loi si t nhin quan trng c dng trong gia cng composite gm c si lanh, ay, gai, tre, da, g Vi nhng u im nh
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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(36).2010

khi lng ring b, tnh nng c l ring cao, t gy tc dng mi mn thit b gia cng, r, thn thin vi mi trng v ngun nguyn liu di do, cc sn phm composite si t nhin c ng dng trong nhiu lnh vc nh: xy dng, giao thng vn ti, ni tht gia dng, vt dng hng ngy, chi tr em Trong s nhng si t nhin, ay l loi si v vn di do Vit Nam cng nh n , Banladest. c bit kh hu nhit i Vit Nam rt thun li cho s pht trin ca cy ay, nn ngun si ay nc ta rt di do, tuy nhin, v ch a c n khai thc s dng trit . Vic nghin cu s dng si ay cng nh cc loi si t nhin khc trong gia cng vt liu composite nc ta ch giai on bt u. Nhng ng dng ca vt liu composite si t nhin trong i sng cng nh trong cng nghip cn rt hn ch. Do vy vic nghin cu ch to v ng dng vt liu composite si ay l rt cn thit. Tuy nhin, vi mt s nhc im nh ht nc ca si tng i cao v tng hp vi nha nn km phn cc tng i thp dn n b m t tip xc gia nha nn v si km bn v do vy tnh nng c l ca composite cha cao lm cho s ng dng sn phm composite si ay ni ring v composite si t nhin ni chung b hn ch. Vic nghin cu ci thin tnh cht ca vt liu composite si t nhin v ang c tin hnh ph bin cc nc trn th gii [1, 2, 3, 4, 5, 6, 7, 8]. nc ta lnh vc nghin cu ny cn rt hn ch. Mt s nghin cu x l b mt si t nhin nhm nng cao tnh nng c l ca composite si tre c thc hin bi mt s nhm nghin cu tuy nhin ch dng mc v m [9, 10, 11]. ci thin tnh nng ca vt liu composite si ay nn nha polypropylene, nghin cu ny thc hin phng php bin tnh nha nn bng cch s dng tc nhn tng hp MAHgPP. Vi nhng phng php phn tch hin i kt hp nhng phng php c bn, nghin cu ny nhm khng ch kho st vt liu mc v m m cn thc hin nhng nghin cu cu trc micro v nano. 2. Tng quan Vt liu composite hay cn gi l vt liu kt hp c hnh thnh t hai hay nhiu vt liu khc nhau, c tnh nng hn hn cc vt liu thnh phn khi s dng ring l. Mi vt liu composite gm mt hay nhiu pha gin on (vt liu gia cng) c phn b trong mt pha lin tc (vt liu nn). Vt liu gia cng c th l si tng hp hoc si t nhin (lanh, ay, gai, tha, x da...) gia cng cho cc vt liu nn khc nhau. Trong , n nha c s dng rt ph bin. Trong nghin c ny, si ay n u c dng lm vt liu gia cng cho nha nn polypropylene. Si ay: c cng v bn ko cao. Vng kt tinh (65-73%) c mc trt t cao lm cho dung mi hoc cc tc cht kh thm nhp. Thnh phn ha hc chnh ca si ay gm: cellulose, hemicellulose v lignin. Nha polypropylene (PP): c tnh nng c l cao, t trng thp v khng phn cc. Mc kt tinh ca PP khong 60-70%, khng ha tan trong bt k dung mi no nhit phng, ch trng v ha tan trong vi dung mi c bit nhit trn 100oC [12].
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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(36).2010

3. Thc nghim 3.1. Nguyn liu v ha cht Si ay mua trn th trng Vit Nam, c cc thng s c bn sau: bn ko 4.31 cN/dtex, xon 300 vng xon/m, mnh 480 tex. Loi nha polypropylene c tn thng mi l HD 120M (PP) c cung cp bi Borealis A/S, CHLB c. Ba loi MAHgPP tc nhn tng h , gm Exxelor PO p 1020 (Ex), Polybond 3200 (Po) v TPPP 8012 (Tp) c cung cp bi cng ty Exxon Mobil Corp., M. Mt vi thng s ca PP v MAHgPP c trnh by trong Bng 1.
Bng 1. Mt s thng s ca cc cht tng hp MAHgPP.

MAHgPP Tnh cht Khi lng ring 23oC (g/cm3) Tc dng chy (g/10 pht) (190oC/1,2 kg) Hm lng anhydride maleic Nhit nng chy ( oC) 3.2. Cc phng php gia cng Mu macro-composite c gia cng qua hai giai on: to compound bng phng php p n v to mu bng phng php c tim. p n o ht compound : Nn nha PP c bin tnh giai on to t compound s dng thit b p n hai trc (Co-rotating twin-screw extruder ZSK 30). Ch nhit ti cc vng nh Hnh 1. p phun to mu composite: Cc ht compound sau khi c sy 4 gi 100oC c dng to mu bng thit b p phun. Mu macro-composite hnh dog-bone c to nn theo tiu chun DIN 53455. Chiu di si trung bnh khong 244 m.
PP + MAHgPP Si ay 165C Chn khng 185C u to hnh 180C

PP Ex 0.908 8 0 180 0.9 125 0.5-1 160 Po 0.91 110 1 160-170 Tp 80 1 -

193C

Hnh 1. Ch nhit s dng my p n.

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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(36).2010

3.3. Kho st tnh cht ca mu composite Th ko trt composite si n: Mu micro-composite c to bng cch cho si n cm thng ng vo chn nh ng polypropylene nng chy 160 oC vi su 50-500 m s dng thit b Embeding ti Vin Nghin cu Vt liu polymer Dresden (IPF), c. Sau khi lm ngui , mu c t trong bnh ht m trong 2 ngy ri tin hnh o ko bn ko trt. Mi php o c thc hin 15-20 mu ly gi tr trung bnh. Th bn c hc: Mu macro-composite hnh dog-bone vi kch thc 160 10 4 mm dng th bn ko theo tiu chun ISO 527-2 v hnh ch nht c kch thc h (20*h) 15 mm c dng th bn un theo tiu chun ISO178 trn thit b Universal testing machine Zwick 1456 ti c. Mu macro-composite kch thc 100 10 4 mm c dng th bn va p trn thit b PSW 4 testing machine ti c theo tiu chun ISO179/1eU. Kho st nh hng ca nc n mu composite: Mu c kch thc nh tiu chun o bn ko c dng ngm trong nc cc nhit 25oC v 70oC trong 7 ngy. Sau thi gian ngm mu c ly ra dng khn giy sch lau kh v xc nh khi lng (bng cn phn tch sai s 10-4g) ghi li s thay i khi lng v o bn ko. Kho st bng knh hin vi in t qut (SEM) v knh hin vi lc nguyn t (AFM): B mt si sau khi ph hy ko trt t micro-composite v ph hy ko t macro-composite c dng kho st hnh thi b mt mc nano (AFM) trn thit b D 3100 v mc vi m (SEM) trn thit b LEO 435 VP, vin nghin cu vt liu polymer Dresden, CHLB c. 4. Kt qu v tho lun 4.1. bn ko trt ca micro-composite: tng tng thch ca nn nha PP khng phn cc vi si ay phn cc, ba loi cht tng hp MAHgPP c dng kho st gm Exxelor PO 1020 (Ex), Polybond 3200 (Po) v TPPP 8012 (Tp). nh hng ca loi v lng cht tng hp (MAHgPP content) n bn ko trt (A pparent interfacial shear strength) ca cc mu micro-composite c trnh by trong th Hnh 2. T th ta thy, khi s dng cht tng hp MAHgPP bin tnh nha nn PP bn ko trt ca mu micro-composite c ci thin. Khi tng hm lng cht tng hp MAHgPP bn ko trt ca mu micro-composite tng. i vi hai cht tng hp Ex v Po th s ci thin khng tng ng k khi s dng hm lng trn 2% khi lng. Trong cc cht tng hp, Ex ci thin ln nht n bn ko trt ca mu si ay/nha PP micro-composite v ti u vi hm lng 2%. bn ko trt tng khong 92% khi s dng 2% Ex so vi mu khng cha Ex. Chng t kt dnh ti b mt tip xc ca nh nn v si tng ln. Ex vi hm lng 2% c xem l a iu kin bin tnh nn ti u trong h composite si ay nn nha polypropylene.
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22

Apparent interfacial shear strength (MPa)

20 18 16 14 12 10 Ex Po TP

2 3 4 5 MAHgPP content (weight %)

Hnh 2. nh hng ca MAHgPP n bn ko trt ca cc mu micro-composite.

4.2. Kho st AFM ca b mt si sau khi o bn ko trt Hnh 3 cho thy ca b mt si ay sau khi o bn ko trt s dng knh hin vi lc nguyn t AFM. B mt si ca mu micro-composite c 2% Ex cho thy c mt PP nhiu hn so vi mu khng cha Ex. C th gii thch l do nn nha PP khng phn c th m t k m ln b mt si ay p h cc tro n g q u trn h gia c ng c n mu, nn PP ch tip xc nhng b mt phng, khng thm vo nhng v tr lm su b mt si. Sau khi ko mu micro-composite, b mt si l ra nhng nhng v tr lm su do khng c nha bm dnh v ch mt vi ch cn nha bm dnh. Tuy nhin, khi s dng 2% Ex th s tng thch gia nn nha v b mt si tt hn, nha thm tt hn vo nhng v tr lm su trn b mt, lin kt hydro v lin kt cng ha tr c th hnh thnh b mt tip xc, trong qu trnh ko trt mu Micro -composite, s ph hy kt dnh ni xy ra ch yu trong nn PP, do vy b mt si sau khi ko dng nh c ph nhiu PP hn.

(a)

(b)

Hnh 3. nh AFM ca b mt si sau khi o bn ko trt mu microcomposite, (a) 0% Ex v (b) 2% Ex.

4.3. bn c hc Hnh 4 cho thy n h hn g ca ch t tng h p Ex v h m ln g si (fibre content) n bn c hc tnh, gm ko (tensile strength) v va p (impact strength)
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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(36).2010

ca mu macro-composite. S s dng Ex vi hm lng 2% lm tng ng k bn ko v bn va p so vi mu khng c Ex. Ring module ko c tng nhng khng ng k khi s dng Ex. i vi mu khng bin tnh, khi tng hm lng si th bn ko gim. Khuynh hng thay i bn ko hon ton khc hn khi tng hm lng si i vi mu c cha Ex, bn tng khi hm lng si tng. Tuy nhin khi hm lng si cao qu th bn li gim (mu c hm lng si 41% th tch).
50 6 5

40

40

30
4

30 3 20 2 10 Do ben keo, 0% Ex Do ben keo, 2% Ex Module keo, 0% Ex Module keo, 2% Ex 40 1 0 0 10 20 30 Fibre content (volume %)

Impact strength (KJ/m2)

Tensile strength (MPa)

Module keo (MPa)

20

10

0 % Ex 2% Ex

0 0 10 20 30 Fibre content (volume %) 40

(a)

(b)

Hnh 4. nh hng ca cht tng hp Ex v hm lng si n bn v module ko (a); bn va p (b) ca mu macro-composite si ay/nha PP.

S s dng si ay gia cng cho nn nha PP lm tng ng k module ko nhng lm gim bn va p ca nha PP. Hm lng si cng tng th bn va p cng gim Hnh 4b v module ko cng tng (Hnh 4a) do tc dng tng cn g ca si. Tuy nhin, hm lng si cao th module ko c khuynh hng gim do lng nha khng thm t, lin kt si v h tr nn km lin tc. 4.4. Kho st knh hin vi in t qut (SEM) Kt qu chp SEM cho thy hnh thi b mt ph hy ca mu Hnh 5.

(a)

(b)

Hnh 5. nh SEM ca mu composite sau khi b ph hy ko, (a) 0% Ex v (b) 2% Ex.

B mt ph hy ca mu composite khng cha Ex c mc kt dnh km ti b mt tip xc gia si v nha nn xut hin nhiu l rng v vt nt vng xung quanh si (Hnh 5a). Tuy nhin, khi n nha c bin tnh bng Ex th kt dnh ti n
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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(36).2010

vng b mt tip xc c ci thin ng k do vy s lng v kch thc cc vt nt v l rng vng ranh gii nha/si gim nhiu (Hnh 5b). 4.5. Kho st nh hng ca nc Hnh 6a cho thy khi hm lng si trong mu tng th hp th nc tng. nhit cao (70oC) mu composite hp th nc mnh hn nhit thp (25 oC). S s dng 2% Ex hn ch ng k s hp th nc, c bit cc mu c hm lng si cao. iu th v khi kt qu cho thy bn ko ca mu PP v composite (Hnh 6b) khng gim hoc thm ch tng nh sau khi ngm trong nc 7 ngy nhit phng 25oC. Tuy nhin, nhit cao 70 oC hu ht cc mu ngm sau 7 ngy u c bn thp hn mu ban u cha ngm. Vi cng iu kin ngm v hm lng si nh nhau, mu composite cha 2% Ex c bn vn cao hn mu khng cha Ex.
6 5 Comp. soi day/PP+2% Ex, 25oC Comp. soi day/PP, 25oC Comp. soi day/PP+2% Ex, 70oC Comp. soi day/PP, 70oC

50

40

Weight gain (%)

4 3 2 1 0 0 10 20 Fibre content (volume %) 30

Tensile strength (MPa)

30
Comp. soi day/PP

20

10

o Comp. soi day/PP, 25 C o Comp. soi day/PP, 70 C Comp. soi day/PP+2% Ex o Comp. soi day/PP+2% Ex, 25 C o Comp. soi day/PP+2% Ex, 70 C

0 0 10 20 Fibre content (volume %) 30

(a)

(b)

Hnh 6: S thay i khi lng (a)v bn ko (b) ca mu sau khi ngm trong nc.

5. Kt lun S x l nha nn ci thin ng k a s cc tnh nng ca vt liu composite. Trong s cc cht tng hp MAHgPP, Ex dng vi hm lng 2% c xem l t i u bin tnh nha nn PP. S s dng Ex lm tng bn ko trt ca mu micro-composite (kho ng 92%), tng ng k bn ko v bn va p, tuy nhin khng lm thay ng k module ko ca mu composite nn nha i polypropylene. Kho st lo ha trong mi trng nc ca mu composite nn nha PP vi thi gian 7 ngy cho thy bn ko khng gim hoc tng nh khi ngm nhit thp (25 oC), tuy nhin khi ngm nhit cao hn (70 oC) bn ko gim. Li cm n: Cm n b Tin s Khoa hc Edith Maeder v ng Tin s ShangLin Gao c nhng ng gp ng k v mt hc thut. Cm n Vin Nghin cu Vt liu polymer Dresden, CHLB c ti tr cho nghin cu ny.

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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(36).2010

TI LIU THAM KHO [1] Bledzki A K, Gassan J. Composites reinforced with cellulose based fibres. Progress in Polymer Science 1999, 24, 221-274. [2] Fung K L, Li R K Y., Tjong S C. Interface modification on the properties of sisal fiber-reinforced polypropylene composites. Journal Applied Polymer Science 2002; 85: 169-278. [3] Mohanty A K, Drzal L T, Misra M. Journal of Materials Science Letters 2002, 21, 1885-1888. [4] Joseph P V, Joseph K, Thomas S, Pillai C K S, Prasad V S, Groeninckx G, Sarkissova M. The thermal and crystallisation studies of short sisal fibre reinforced polypropylene. [5] Feng D, Caulfield D F, Sanadi A R. Effect of compatibilizer on the structureproperty relationships of kenaf-fiber/polypropylene composites. Polymer Composites 2001, 22, 4, 506-517. [6] Sanadi A R, Caulfield D F. Transcrystalline interphases in natural fibre-PP composites: effect of coupling agent. Composite Interfaces, 2000, 7 (1), 31-43. [7] Qiu W, Zhang F, Endo T, Hirotsu T. Preparation and characteristics of composites of high-crystalline cellulose with polypropylene: effects of maleated polypropylene and cellulose content. Journal of applied Polymer Science, 2003, 87, 337-345. [8] Rana A K, Mandal A, Bandyopadhyay S. Short jute fibre reinforced polypropylene composites: effect of compatibiliser, impact modifier and fibre loading. Composites Science Technology, 2003, 63, 801-806. [9] Phan Th Minh Ngoc, Cao Hong Long, Nghi n c ch to vt liu polyme u compozit trn c s phenol -focmandehit gia cng bng phoi tre, Tp ch ha hc T43-1/2005. [10] Trn Vnh Diu, Nguyn Phm Duy Linh, o Minh Anh, Nghin cu nh hng ca x l b mt si tre bng anhydric axetic n tnh cht ko ca vt liu polyme compozit trn c s nha polypropylen, Tp ch ha hc, T43-4/2005. [11] Trn Vnh Diu, Phm gia Hun, Phm Xun Khi, Nghin cu qu trnh x l b mt si tre bng acrylonitril (AN) v tnh cht ca vt liu polyme compozit trn c s nha polypropylen gia cng bng si tre. Tp ch ha hc T43-5/2005. [12] Polymerwerkstoffe- lecture from Prof. Heindrich, IPF Dresden, Germany.

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