Tgp chi Hoa hgc,
T. 48(6), Tr. 774 - 779, 2010
NGHIEN CLTU HE EPOXY DER-331 DONG RAN BANG METYLTETRA HYDRO PHTALIC ANHYDRIT (MTHPA)
DE CHE TAO VAT LIEU COMPOZIT TIEN TIEN
PHAN II - ANH Hl/CJNG C O A N A N O C L A Y DEN S J DONG RAN C O A
HE EPOXY DER-331/MTHPA/DMP-30
De'n Tda sogn 26-01-2010
LE HOAl ANH', BUI CHUONG', TRAN N H U T H O ' , VU DINH KHIEM', DINH THI LIEN' 'Vien Ky thudt Hda Sinh vd Tdi lieu Nghiep vu (El 7) - Bd Cdng an
'Trung tdm Nnghien cUu vdt lieu polyme, Trudng Dgi hgc Bdch khoa Hd Ngi
^Vien Khoa hgc & Cdng nghe Qudn su - Bd Qud'c phdng
ASBTRACT
Nanoclays were added to DER-331 epoxy cured with metyltetra hydro phatalic anhydride (/MTHPA) and DMP-30 catalyst. Effect of adding nanoclay to the epoxy on cure reaction of the composites was studied by measuring gel contents. X-ray diffraction (XRD) technique was employed to investigate the inter-planar distance between the nanoclay platelets in different samples. Scanning electron microscopy (SEM) was used to investigate the morphology of composites. The mechanical properties of the composites were characterized in terms of tensile, flexural and compression tests. The results show that adding nanoclay to the epoxy composites decreases the gel contents of epoxy hut increases the mechanical properties of the epoxy composites by 16% in tensile, 10% in compression and 16% in flexural strength.
I - MC) DAU cudng bang vai cacbon thi do bin udn da tang tQ 306 MPa len 383 MPa, modun tang tQ 35 GPa NhQng nam gdn day, da cd nhilu cdng trinh iSn 40 GPa, modun tfch trQ tang 52%, nhiet dd khoa hgc nghien cQu vl vat lieu nanoclay thuy tinh tang len 13°C (tQ 82°C ien 95°C) [4].
polyme compozit ndi chung va vat lieu nanoclay Yuan Xu, Suong Van Hoa da su 4% nanoclay polyme compozit tren co sd nhya epoxy ndi trong he epoxy ddng rdn bdng 4,4'- rieng. Cac cdng trinh nghien cQu da chQng minh diaminodiphenylsulfone (DDS) gia cudng bdng rdng, ehl vdi mdt ham Mgng rat nhd vai phdn sgi cacbon. Kit qud cho thdy, do bin udn cua tram trgng Mgng nanoclay thi vat lieu polyme vat lieu da tang 38% vd dd dai va dap tang 85%
compozit tren nin nhya epoxy da mang lai nhilu so vdi ban ddu [5].
tfnh chat uu viet ban so vdi ban ddu. Tfnh chdt Tuy nhien, ben canh nhung tac dung tfch CO hgc, tfnh chat nhiet, kha nang chd'ng chdy, eye thi vat lieu ndy cung gay nen nhQng ban che ben hod chdt, chd'ng thdm khf... diu tang len [1 - iam giam mgt sd tfnh chat cua vat lieu ban ddu.
3]. F. H. Chowdhury vd cdc ddng nghiep su Nguyen nhan la do vdi mdi loai nanoclay thi dyng 2% nanoclay trong he epoxy-nanoclay gia qua trinh e h l tao, bie'n tfnh khde nhau ddn den 774
kha nang tuang hap vdi vat lieu eung khac nhau
[1,2]. • - 5
Chung toi da nghien cQu va tim dugc dilu kien ddng rdn he DER-331/MTHPA/DMP-30 cd cac tfnh chdt tdt nhat vdi ty le moi MTHPA/DER-331 la 0,75/1 va DMP-30/DER- 331 Id 0,0028/1 d nhiet do 115°C trong 3 gid.
Bdi bdo ndy trinh bay cdc kit qua nghien cQu vl anh hudng cua nanoclay din nhiet do ddng rdn cung nhu thdnh phdn cdc cdu tQ trong he. Mdt sd tfnh chdt cua he cd nanoclay cung dugc khdo sdt.
II - THUC NGHIEM 1. Nguyen lieu va hoa chat
- Nhya epoxy DER-331 cua hang Dow Chemicals (Hoa Ky) cd dugng Mgng epoxy 188,6 g/mol, do nhdt d 25°C: 1.348 poise.
- Chdt ddng rdn metyltetra hydro phtalic anhydrit (MTHPA) cua hang Dow Chemicals (Hoa Ky) cd khdi Mgng duong Mgng anhydrit:
166, do nhdt d 25°C: 0,6 poise.
- Chat xuc tdc ddng rdn 2, 4, 6 tri(dimetyl amino metyl) phenol (DMP-30) dugc tdng hgp cd khdi lugng phan tu: 265, ham lugng amin bae 3: 15,85, do nhdt d 25°C: 3 poise.
- Nanoclay I28E va I30E cua hang Nanocor (Hoa Ky).
- Nanoclay 6A cua hang Southclay (Hoa Ky).
2. Che tao vat lieu
Nanoclay dugc dua vdo nhya epoxy DER- 331 va khudy vdi td'c do 2000 vdng/phut trong 2 gid, sau dd dugc trgn vdi MTHPA vd DMP-30 theo ty le dinh trade. Mdu dugc hut chan khdng dl loai bd hit bgt khf va cho ddng rdn d nhiet do quy dinh.
3. Phuong phap nghien cihi
- Ham lugfng phan gel dugc xac dinh bdng each trich ly trong axeton tren dyng cu xoxblet trong 16 gid.
- Phd nhilu xa tia X dugc ghi tren may Siemens D5005.
- Anh SEM dugc chyp tren may JSM-6868 LV, JEOL (Nhat Ban). Ngudn bQc xa cd hieu dien t h i 25kV, mQc do phdng dai 10.000 lan.
- Tfnh chat eg hgc: Do bin udn dugc xdc dinh theo tieu chuan ISO 178 1993 (E), do bin nen xdc dinh theo tieu chuan ISO 604 1993 (E), do bin keo dugc xdc dinh theo tieu chuan ISO 3268 1978 (E) tren may Tinius Olsen HIOOKT Hounfield, tdc do keo 2 mm/phut.
Ill - KET QUA v A T H A O LUAN 1. Phd XRD cua cac m i u epoxy
Tren hinh 1 trinh bdy phd XRD cua cac mdu epoxy vdi cdc nanoclay DOE, I28E vd 6A.
Kit qud tfnh khoang each ca sd d cua cac nanoclay tren tQ phd XRD dugc trinh bdy trong bang 1.
Bdng 1: Khodng cdch d cua cdc mdu nanoclay trade vd sau khi phan tdn vao nin epoxy
STT 1 2 3
Mau I28E I30E 6A
Khoang cdch ca sd d,oo, A 23,338
26,715 37,11
Khoang each sau khi phan tdn vdo pha nin, A
37,55 Trdc ldp
35,46 Cdc kit qua tren cho thdy, vdi phucmg phap
trgn eg hgc nhu tren, ehi cd I28E vd DOE cd khd nang phan tan xen ke hoac trdc ldp trong nin epoxy DER-331.
2. Anh hudng cua nanoclay den nhiet do dong ran
Nhua epoxy DER-331 dugc trgn vdi 3 phdn khdi Mgng (PKL) nanoclay va ddng rdn bdng MTHPA vdi ty le moi MTHPA/DER-331 la
0,75 vd DMP-30/DER-331 la 0,0028. Khao sdt 115°C din 190°C. Kit qua dugc trinh bay d ham lugng phan gel d cdc nhiet do ddng rdn tQ hinh 2.
VNU-HN-SIEMENS DSOOS - NanoOiy I -ME
A
VNU-Hht-SIEMENS D9(K» - rtBlwCtay- I2SE
Z-TYwta • Seal*
VNU-MN-SIEMENS 05005 - NaiwClay-1 JSE |1i5) VNU-HH-KEMEKS D5005 • ManoClay- 6A |130|
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Hinh 1: Phd XRD cua nanoclay DOE(a), I28E(b) vd 6A(c) va cdc mdu tucmg Qng sau khi phan tan trong nin epoxy: I30E(d), I28E(e) vd 6A(f)
776
c
-«B
a.
Ol
c j
£
-(0
100 95 90 85 - 80 - 75 70 -\
65 60
-I30E -I28E
110 120 130 140 150 160 Nhiet do. "C
170 180 190
Hinh 2: Anh hudng cua nanoclay din ham lugng phdn gel d cdc nhiet dd ddng rdn khde nhau
Cd thi nhan thdy khi dua nanoclay vdo hdm lugng phdn gel cua he gidm di so vdi khi khdng cd nanoclay: Mdu vdi DOE dat 88,3% vd mdu I28E dat 80,4%. Ngodi ra, nhiet do ddng rdn Qng vdi phdn gel cao nhdt cung tang: Vdi mdu ed DOE, nhiet dd nay dat tdi 160°C nghia Id tuang duang vdi mdu khdng cd DMP-30. Mdu I28E tuy cd phdn gel dn dinh tQ 115°C nhung cung khdng -vugt qud 80%. Dilu nay chQng td viec dua nanoclay vao lam giam mQc do ddng rdn cua he DER-331/MTHPA/DMP-30.
3. Anh hudfng nanoclay de'n he dong ran va xiic tac dong rdn
Viec giam ham Mgng phdn gel va tang nhiet do ddng rdn khi dua nanoclay vdo he cd thi do nanoclay Mang tdc vdi cdc chat ddng rdn vd xuc tdc ddng rdn lam gidm boat tfnh cua cac chat nay. De kiem tra gid thilt nay, da khdo sdt dnh hudng cua nanoclay din hdm lugng phdn gel khi thay ddi lugng ddng rdn MTHPA (hinh 3) vd DMP-30 (hinh 4). Trong ed hai tradng hgp nhiet do ddng rdn la 115°C, thdi gian 3 gid, ham Mgng nanoclay la 3 PKL.
0)
c
£
a
0) c b-
3
•IB
I 84 82- 80 78 76 74
0,7 0.8 0.9
Tyle moi IVITHPA/DER-331
1,1
Hinh 3: Anh hudng eua MTHPA den ham lugfng phdn gel (ty le moi DMP-30/DER-331 = 0,0028/1)
96
•zn-
TvleiiiolDMP-30/Dm-331
Hinh 4: Anh hudng cua DMP-30 din ham Mgng phdn gel (Ty le moi MTIIPA/DER-331 = 0,75/1) Kit qua tren hinh 3 cho thdy, mac du ty le
MTHPA/DER-331 thay ddi ttong mgt khoang rdng nhung ham lugng phdn gel cM dat tdi khodng 82% den 84%, nhd ban so vdi kM khdng cd nanoclay (94% din 95%). Cd nghia Id nanoclay ft anh hudng din lugng MTHPA du, do dd viec gidm mQc do ddng rdn ft phy thugc vao MTHPA.
Cung tuang ty, khi Mgng DMP-30 nhd (0,0028 mol/mol epoxy), ham Mgng phdn gel cua mdu cd nanoclay I28E chi dat 80% (so vdi 95% cua mdu khdng cd nanoclay), cdn mdu vdi DOE tham chf cdn thdp ban (hinh 4). Tuy nhien, khi lugng DMP-30 du ldn (0,0042 moi ttong mdu vdi I28E vd 0,0105 moi trong mdu vdi DOE), ham lugng phdn gel da dat tdi 92 - 95%, tuong dugng mdu vdi 0,0028 moi DMP-30 vd khdng cd nanoclay (hinh 4).
Nhu vay, sy gidm hdm Mgng phdn gel khi dua nanoclay vao he epoxy Id do Mcmg tdc giQa nanoclay vd DMP-30. D l tim hieu ban chat Mang tac ndy, chung tdi da chyp phd hdng ngoai cac hdn hgp DMP-30/I30E, DMP- 30/I28E. Kit qua cho thdy, so vdi phd IR cua DMP-30, DOE, I28E, phd cua hdn hgp DMP- 30/I28E va DMP-30/I30E khdng cd them pic dac trang ndo mdi. Dilu ndy chirng td giua nanoclay va DMP-30 khdng cd tuang tdc hda hgc. Neu chu y rdng nanoclay dugc biln tfnh bl
mat bdng cac alkyl amin, cd thi gia thilt mdt phdn DMP-30 da bi hdp phy bdi cdc ldp nanoclay do dd tac dung xuc tac ddng rdn giam di. DOE dugc biln tfnh bdng mudi octadexyl amoni (amin bae bd'n) cd do axit Lewis cao han I28E biln tfnh bdng amin bae hai (octadecyl amin) se hdp phy DMP-30 manh ban. Chi khi bd sung DMP-30 du d l bu ddp lugfng hao hut do hdp phy, hdm lugng phdn gel mdi dat mQc nhu khdng cd nanoclay. Cung vi If do tren, lugng DMP-30 cdn thiet bd sung vao mdu cd DOE cao han hdn so vdi mdu cd I28E.
4. Tinh chat co hoc va caiu triic hinh thai vat lieu epoxy - nanoclay
Viec dua nanoclay vao cd tdc dyng tang cudng tfnh chat ca hgc cua he nhua epoxy (bang 2).
Sy tang tfnh chai cung cd the nhan thdy khi quan sdt b l mat gay cua mdu cd va khdng cd nanoclay (hinh 5).
Qua cac dnh SEM nhan tha'y rd su khac nhau trong cau true bl mat cua mdu pha nin cd va khdng cd nanoclay DOE. Mdu pha nin khdng cd nanoclay DOE cd cdu tnic chua bin chat, be mat mdu cdn nMlu nhap nhd vd cdc hat thd.
Mdu pha nen cd nanoclay DOE chi vdi 3PKL nhung cdu true da bin chat ban ddng ke, nanoclay DOE da lam gidm dugc cdc hat thd va
san phang nhung nhdp nhd tren bl mat. Kit qua ban e h l gay ra nhung vlt mil do Qng suat ndi tQ nay tao sy dong nhdt trong cau true cua pha nin, dd cdi thien cdc tfnh chdt ca hgc.
Bdng 2: Tinh chat eg hgc cua he epoxy ed vd khdng cd nanoclay
STT
1 2
Mdu
DER-331/MTHPA/DMP-30/I30E DER-33 l/MTHPA/DMP-30
Tfnh chat ca bgc Dd bin keo
dQt, MPa 36,42 31,53
Do bin nen, MPa 75,89 68,70
Do ben udn, MPa 72,96 63,12
• • » ' - '•il' . - , • • - •
-Oi a
1 •• f" .
'f«
Wi
(a) (b) Hinh 5: Anh SEM b l mat gay mdu epoxy khdng cd (a) va cd nanoclay I30E(b)
IV - KET LUAN
1. Khi dua nanoclay vdo he epoxy DER- 33 l/MTHPA/DMP-3 mQc do ddng idn cua he giam xud'ng. Sy giam ndy cd the gidi thfeh la do mgt phdn DMP-30 da bi hdp phy bdi nanoclay cd bl mat biln tfnh amin.
2. Nanoclay DOE cd tdc dyng tang cdc chi tieu do bin cua he epoxy ndi tien. Khao sdt sa bg cho tha'y vdi 3PKL DOE, cdc chi tieu do ben tang khoang 10% - 16%).
T A I LIEU THAM K H A O
1. Jinwei Wang, Shuchao Qin. Materials 5.
Letters, Vol. 61, 4222 - 4224 (2007).
Lei Wang, Ke Wang, Ling Chen, Yongwei Zhang, Chaobin He. Composites Part A:
Applied Science and Manufacturing, Vol.
37, 1890 - 1896 (2006).
F. Carrasco, P. Pages. Polymer Degradation and Stability, Vol 93, P. 1000 - 1007 (2008).
F. H. Chowdhury, M. V. Hosur, S. Jeelani.
Material Science and Engineering A, Vol.
421,298-306(2006).
Yuan Xu, Suong Van Hoa. Composite Science and Technology, Vol. 68, 854 - 861 (2008).
Lien he: Bui Chuong
Trung tam NCVL POLYME, Tradng Dai hgc Bach khoa Ha Ngi 1 Dai Cd Viet, Ha Ndi.
Email: [email protected]
