TP CH KHOA HC V CNG NGH, I HC NNG - S 1(42).

2011

NGHIN CU CH TO VT LIU NANOCLAY COMPOSITE TRN NN NHA POLYESTER KHNG NO

INVESTIGATION ON PROCESSING NANOCLAY COMPOSITE BASED ON UNSATURATED POLYESTER MATRIX on Th Thu Loan H Vit Lc Nguyn Minh Hong

Trng i hc Bch khoa, Lp Cao hc Ha Hu C 08, Trng i hc Bch khoa, i hc Nng Trng i hc S phm, i hc N i hc Nng

TM TT Nanocomposite trn c s nha polyester khng no (UPE) v nanoclay vi cc hm lng khc nhau (1, 2 v 3% khi lng (%kl)) c ch to. Bng cc phng php kho st: Nhiu x tia X (XRD), knh hin vi in t truyn qua (TEM) v o tnh cht c l xc nh c hm lng nanoclay ti u l 2%kl. Nanocomposite vi hm lng nanoclay ti u tng 15,27% bn ko v 17,01% bn un so vi mu nha UPE. Hn na, s c mt nanoclay ci thin ng k bn c l v mi trng (nc my, nc bin, NaOH v HCl) ca vt liu composite t nha UPE v si thy tinh. ABSTRACT Nanocomposites were prepared based on unsaturated polyester (UPE) and nanoclay with different amount (1, 2 and 3 weight % (wt%)). By using different analysis methods, such as X-ray diffraction (XRD), transmission electron microscopy (TEM) and mechanical testing, the optimal content of nanoclay in UPE nanocomposite determined is 2 wt%. UPE nanocomposite with optimal content of nanoclay improved 15.27% tensile strength and 17.01% flexural strength comparing to pure UPE sample. Furthermore, Mechanical properties and environmental resistance (water, sea-water, NaOH and HCl) of glass fiber reinforced UPE composite significantly improved while adding 2 wt% nanoclay.

1. t vn Hin nay trn th gii c nhiu nghin cu v vt liu composite nanoclay nn polymer sau khi khm ph ra s ci thin ng k tnh cht ca polymer khi c mt ca cc ht clay kch thc nano [1, 2]. Cc nghin cu cho thy rng s c mt ca clay kch thc nano lm tng bn v modul [3], gim kh nng thm [4, 5], gim co ngt [6]... i vi polymer. Ring Vit Nam, nhng nghin cu v vt liu nano ni chung v vt liu nanoclay composite ni ring vn cn rt hn ch [7, 8], mc d ngun nguyn liu clay nc ta kh phong ph. Mt s cng ty khai thc ngun clay ti Nha M (Bnh Thun), Duy Linh (Lm ng)... sn xut nanoclay thng phm vi gi r hn nhiu so vi cc loi vt liu c kch thc nano khc v cc ngun nguyn liu nano ngoi nhp. Chnh v vy, vic nghin cu ch to vt liu nanoclay composite v kho st s nh hng ca nanoclay n cc tnh cht ca composite truyn thng nn nha UPE gia cng si thy tinh l rt cn thit.
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2. Thc nghim 2.1. Nguyn liu Nha Polyester khng no s dng l loi 2117 sn xut Singapore. Si thy tinh dng mat 300 g/m2 do Trung Quc sn xut. Nanoclay hu c c sn xut ti Vit Nam bi cng ty TNHH Minh H. Nc bin ly ti bi bin Xun Thiu, Nng. 2.2. Ni dung v phng php nghin cu 2.2.1. Nghin cu nanocomposite trn c s nha UPE v nanoclay 2.2.1.1 Kho st nh hng ca thi gian siu m n s phn tn nanoclay trong UPE Phn tn nanoclay (2% kl) trong nha UPE vi cc khong thi gian: 0,5; 1 v 1,5 gi bng my siu m Utrasonic Processor 750W Model. Sau , ln lt quan st v chp nh di knh hin vi quang hc Olympus phng i 1000 ln ti Phng th nghim Vi sinh, trng i hc Bch khoa Nng. 2.2.1.2. Kho st s phn tn nanoclay trong nha UPE bng XRD ng nht siu m hn hp nanoclay v nha vi hm lng nanoclay l: 1, 2 v 3%kl thi gian ti u ri to mu vi kch thc 100 100 2 (mm3), ng rn 72 gi nhit phng v sau sy 700C trong 3 gi ng rn hon ton. Mu c o XRD ti Phng th nghim trng im Polymer Composite, i hc Bch khoa thnh ph H Ch Minh. 2.2.1.3. Kho st tnh cht c l ca nanocomposite ng nht siu m hn hp nha v nanoclay, sau to mu vi khun c kch thc ( 200 200 4 ) mm3, ng rn 72 gi nhit phng v sy 700C trong 3 gi ng rn hon ton. Cc mu c o c l: o bn ko theo tiu chun ISO 3268, o bn un theo tiu chun ISO 178-1975 bng my UH-500 KNI Shimadzu ti Phng th nghim Sc bn vt liu, trng i hc Bch khoa Nng. 2.2.2. Nghin cu composite trn c s nha UPE gia cng bng si thy tinh v nanoclay 2.2.2.1. Gia cng mu composite - Chun b: Lm sch b mt khun, ph lp chng dnh ln khun. Si thy tinh c ct theo hnh dng khun v c sy 1050C trong 15 pht. Cn khi lng nha v si theo t l nha/si l 60/40 [9]. - Gia cng: Trn cht xc tc ng rn vo nha (c v khng c clay). Tin hnh p ln lt tng lp si v ln nha tht k vo mi lp nha thm t u si v trnh s to thnh bt kh. Sau khi ln xong, cho mu ng rn trong 72 gi nhit phng v sau sy 700C trong 3 gi.
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2.2.2.2. Kho st bn v s thay i khi lng ca mu trong cc mi trng Cc mu c ngm trong cc mi trng: nc my, nc bin, NaOH (10%), v HCl (10%) trong thi gian l 30 ngy nhit phng. Theo thi gian, mu c ly ra v xc nh thay i khi lng. Sau tin hnh o: bn ko theo tiu chun ISO 3268, bn un theo tiu chun ISO 178-1975 ca cc mu composite trc v sau khi ngm. 2.2.2.3. Kho st b mt ph hy ca mu composite bng SEM Mu composite c cha v khng cha nanoclay sau khi o bn ko c chp di knh hin vi in t qut xem xt b mt ph hy ca mu. Php o c thc hin ti Vin Khoa hc v Cng ngh Vit Nam, theo tiu chun o ISO 10360. 3. Kt qu v tho lun 3.1. Nanocomposite trn c s nha UPE v nanoclay 3.1.1. nh hng ca thi gian siu m n s phn tn nanoclay trong nha UPE Hn hp UPE v nanoclay sau khi ng nht siu m c quan st di knh hin vi thu c kt qu nh sau (hnh 3.1):

(b)

(c)

Hnh 3.1. nh chp knh hin vi quang hc ca hn hp nha UPE v 2%kl nanoclay sau khi ng nht siu m vi thi gian 0,5 gi (a); 1 gi (b) v 1,5 gi (c).

Da vo cc hnh 3.1a, b, c cho thy rng thi gian siu m ti u l 1 gi. Khi siu m trong thi gian 0,5 gi th cc mch phn t nha UPE ch yu xen ln gia cc ht nanoclay, cc kt t vn cn nhiu. Khi siu m trong thi gian di hn (1 v 2 gi) th dng nh khng cn cc kt t na chng t s phn tn tt ca nanoclay trong nn nha UPE (hnh 3.1b, c). 3.1.2. Ph nhiu x tia X ca nanocomposite t UPE v nanoclay Kt qu XRD ca cc mu c th hin hnh 3.2.

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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(42).2011

Hnh 3.2. Ph nhiu x tia X ca nanoclay (a), nanocomposite UPE+2%kl nanoclay (b).

Trn ph nhiu x tia X ca clay xut hin cc peak ti gc 2 l 2,40 v 3,80 tng ng vi cc khong cch gia cc lp clay sau khi bin tnh bng hp cht hu c l 4,07nm v 1,97 nm do cc phn t cht hu c xen vo gia cc lp clay lm tng khong cch c bn ca clay ban u (d001=1,19 nm). Sau khi phn tn trong nha UPE bng phng php ng nht siu m th cc peak ny khng cn na v dch chuyn v pha gc nh, tc khong cch gia cc lp clay gia tng v c khuynh hng tch lp. iu ny cho thy s phn tn cc ht nanoclay t c hiu qu chn tch tt trong nn nha UPE. 3.1.4. Hin vi in t truyn qua ca nanocomposite t UPE v nanoclay Kt qu TEM ca mu nanocomposite trn c s UPE vi hm lng nanoclay: 1%kl, 2%kl, 3%kl c th hin hnh 3.3. Cng vi kt qu nhiu x tia X (hnh 3.2), kt qu kho st hin vi in t truyn qua (hnh 3.3) khng nh vt liu nanocomposite trn c s UPE v nanoclay c phn tn bng phng php ng nht siu m c cu trc tch lp. Cc mch i phn t nha UPE chn vo gia cc lp clay v phn ln cc lp clay b bc tch.

(a)

(b)

(c)

Hnh 3.3. nh TEM ca mu nanocomposite trn c s UPE v nanoclay vi cc hm lng nanoclay: 1%kl (a), 2%kl (b) v 3%kl (c).

3.1.3. Tnh cht c l ca nanocomposite t UPE v nanoclay bn ko v un ca nanocomposite vi cc hm lng nanoclay 1, 2 v 3%kl c trnh by hnh 3.4.
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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(42).2011

80

60

Do ben (MPa)

40

20 D o b e n k e o (M P a ) D o b e n u o n (M P a ) 0 1

H a m lu o n g n a n o c la y ( % k l)

Hnh 3.4. nh hng ca hm lng nanoclay n bn ko v bn un.

Da vo hnh 3.4 cho thy rng, hm lng nanoclay ti u l 2%kl v vi hm lng ti u ny nanocomposite tng 15,27% bn ko v 17,01% bn un so vi mu nha UPE. 3.2. Composite trn c s nha UPE gia cng bng nanoclay v si thy tinh 3.2.1. Tnh cht c l bn ko v un ca composite UPE gia cng si thy tinh v composite UPE gia cng nanoclay kt hp si thy tinh c th hin hnh 3.5.
300 250 200 150 100 50 0 D o ben keo D o ben uon

Do ben (MPa)

U P E /T h u y t in h

U P E + n a n o c la y / T h u y tin h

Hnh 3.5. bn ko, bn un ca composite UPE/si thy tinh v composite UPE+nanoclay/si thy tinh

Da vo hnh 3.5 c th thy rng composite UPE+nanoclay/si thy tinh c bn ko tng 14,98%, bn un tng 16,13% so vi composite UPE/si thy tinh, chng t s c mt ca nanoclay ci thin nh bn c l ca composite UPE/si thy tinh. 3.2.2. Kho st b mt ph hy ca mu sau khi o bn ko bng SEM Hnh 3.6 cho thy nh SEM ca cc mu composite trn c s UPE/si thy tinh (ti u) v UPE + nanoclay/si thy tinh (ti u).

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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(42).2011

Hnh 3.6. Kt qu SEM ca mu UPE/si thy tinh (a),UPE+nanoclay/si thy tinh (b)

nh chp SEM cho thy vi mu UPE/si thy tinh khng c nanoclay (hnh 3.6a) th b mt si thy tinh trn v c nhiu khe nt ti b mt tip xc gia nha v si thy tinh iu chng t nha bm vo si cha tt. Tuy nhin, i vi mu UPE+nanoclay/si thy tinh (hnh 3.6b) th b mt si nhm hn v cn dnh mt t nha, ng thi c t vt nt hn ti b mt tip xc gia nha v si thy tinh. iu ny chng t rng khi c mt 2%kl nanoclay s bm dnh ca nha vo b mt si thy tinh tt hn, gp phn lm tng bn c l v chu mi trng ca vt liu composite. 3.2.2. Kh nng chu mi trng ca cc mu composite 3.2.2.1. S thay i khi lng cc mu composite khi ngm trong cc mi trng Cc ng cong biu din s thay i khi lng mu composite nn nha UPE gia cng si thy tinh, c v khng c nanoclay khi ngm trong cc mi trng khc nhau (hnh 3.7) cho thy thay i khi lng trong mi trng gim dn nh sau: NaOH > HCl > nc bin> nc my. S c mt ca nanoclay lm gim ng k thay i khi lng ca mu composite.
4 U P E / s o i t h u y t in h U P E + n a n o c la y / s o i t h u y t in h Thay doi khoi luong (%) 3

(a)
Thay doi khoi luong (%) 3

U P E / s o i t h u y t in h U P E + n a n o c la y / s o i t h u y t in h

(b)

0 0 10 20 T h o i g ia n n g a m ( n g a y ) 30

0 0 10 20 T h o i g ia n n g a m ( n g a y ) 30

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TP CH KHOA HC V CNG NGH, I HC NNG - S 1(42).2011

4 U P E / s o i t h u y t in h U P E + n a n o c la y / s o i t h u y t in h Thay doi khoi luong (%) 3 4

(c)
Thay doi khoi luong (%) 3 2

U P E / s o i t h u y t in h U P E + n a n o c la y / s o i t h u y t in h

(d)

0 0 10 20 T h o i g ia n n g a m ( n g a y ) 30

0 0 10 20 T h o i g ia n n g a m ( n g a y ) 30

Hnh 3.7. thay i khi lng cc mu composite khi ngm trong cc mi trng nc my (a), nc bin (b), NaOH 10% (c) v HCl 10% (d).

3.2.2.2. bn cc mu composite sau khi ngm trong cc mi trng bn ko v un ca cc mu composite trc v sau khi ngm 30 ngy trong cc mi trng c th hin hnh 3.8.
150

U P E /s o i th u y tin h U P E + n a n o c la y/s o i th u y tin h

350

(a)

300 250

U P E / s o i t h u y t in h U P E + n a n o c la y / s o i t h u y t i n h

(b)

Do ben keo (MPa)

50

Do ben uon (MPa)

100

200 150 100 50

0 T ru o c n g a m N uoc m ay N u o c b ie n N aO H HCl

0 T ru o c n g a m Nuoc m ay N u o c b ie n N aO H HCl

Hnh 3.8. bn ko (a) v bn un(b) ca composite UPE/si thy tinh v composite UPE+nanoclay/si thy tinh trc v sau khi ngm 30 ngy trong cc mi trng.

Da vo hnh 3.8 c th thy rng bn ca vt liu composite gim dn trong cc mi trng: nc my, nc bin, HCl, NaOH. S c mt ca nanoclay trong cu trc composite lm tng ng k bn mu composite trong cc mi trng. Vi cu trc dng lp, nanoclay ng vai tr l cc tm chn ngn hu hiu chn s thm nhp ca cc thnh phn thp phn t t mi trng vo bn trong cu trc vt liu v ngc li, do vy hn ch s thay i khi lng (do trng v tan) v hn ch c s gim bn ca mu composite khi ngm trong cc mi trng. 4. Kt lun Vi phng php ng nht siu m trong thi gian 1 gi phn tn tt cc ht nanoclay trong nn nha UPE. Cc kt qu nghin cu cho thy s s dng 2%kl nanoclay so vi nha ci thin nh tnh cht c l ca vt liu nanocomposite trn nn nha UPE. Hn na, tnh cht c l v kh nng chu mi trng ca composite nn nha UPE v si thy tinh cng tng ln khi c mt ca 2%kl nanoclay.

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TI LIU THAM KHO [1] A.Usuki,M. Kawasumi, Y. Kojima, A.Okada, T. Kurauchi, and O. Kamigaito (1993), Swelling behavior of montmorillonite cation exchanged for -amino acids by -caprolactam, Journal of Materials Research, vol. 8, no. 5, pp. 11741178. [2] A. Usuki, Y. Kojima, M. Kawasumi, et al. (1993), Synthesis of nylon 6-clay hybrid, Journal of Materials Research, vol. 8, no. 5, pp. 11791184. [3] Y. Kojima, A. Usuki, M. Kawasumi, et al. (1993), Mechanical properties of nylon 6-clay hybrid, Journal of Materials Research, vol. 8, no. 5, pp. 11851189. [4] K. Yano, A. Usuki, A. Okada, T. Kurauchi, and O. Kamigaito (1993), Synthesis and properties of polymide-clay hybrid, Journal of Polymer Science Part A: Polymer Chemistry, vol. 31, no. 10, pp.24932498. [5] Y.Kojima, K.Fukumori, A.Usuki and T.Kurauchi (1993), Gas permeabilities in rubber-clay hybrid, Journal of Materials Science Letters, vol.12, no.12, 889890. [6] E. Haque and C. D. Armeniades (1986), Montmorillonite polymer concrete: zeroshrinkage and expanding polymer concrete with enhanced strength, Polymer Engineering & Science, vol. 26, no. 21, pp. 15241530. [7] Thi Hong, Nguyn Thc Kim, Quang Thm, Nguyn Tin Dng, L nh Ngc Kh nng chy nht, cu trc v tnh cht c l ca vt liu compozit polyvinyl clorua/nanoclay, Tp ch Khoa hc Cng ngh, tp 44, s 2, 2006, 18-23. [8] Ha Thuc Chi Nhan, Tran Mai Anh, Laurent Reinert, Laurent Duclaux, Huy Ha Thuc Modification of purified Vietnamese clay by the polyol surfactants application for the elaboration of polyurethane nanocomposites, Asian Workshop on Polymer Processing 2010, 318-328, December 7-10, 2010 Hanoi, Vietnam. [9] Nguyn Th Hng (2009), nh gi bn ca vt liu composite trn c s nha Polyester khng no gia cng bng si thy tinh trong mi trng nc bin, i hc Nng, Lun vn tt nghip.

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