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Tap ch Khoa hoc Trng ai hoc C n Th Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

NHA PHN HY SINH HC POLY (LACTIC ACID) TNG QUAN V NG DNG


Phng Thanh V1, Trn Cng Huyn1, ng Th Cm Tin1 v Phm Ngc Trc Qunh1
1
Khoa Cng ngh, Trng i hc Cn Th

ABSTRACT
Thng tin chung:
Ngy nhn: 16/06/2015 Polylactic acid (PLA) is made from a natural resource - corn starch and
Ngy chp nhn: 27/10/2015 formulated from the condensation polymerization of D- or L- lactic acid
or ring opening polymerization of the lactide. It is completely
Title: biodegradable, compostable, and can maintain its mechanical properties
Biodegradable Poly (lactic without rapid hydrolysis even in high humidity conditions. In this review,
acid) (PLA): Overview and we study and explain why Poly (lactic acid) is considered as one of the
Applications most environment-friendly biodegradable thermoplastic polyesters with
extensive applications.
T kha:
TM TT
Nha nhit do, nha phn
hy sinh hc, tinh bt ng, Nha Poly (latic acid) (PLA) c sn xut t tinh bt ng bng qu
poly(lactic acid) PLA trnh trng ngng D- hoc L-lactic acid hoc m vng Lactide. y l
loi vt liu phn hy sinh hc, c kh nng phn ha v c th duy tr
Keywords: c tnh k c trong iu kin m cao. Chnh v l do , bi bo ny
Biodegradable plastic, corn- s tng hp v trnh bi l do ti sao Polylactic acid li c quan tm
starch, thermoplastic, poly nh vt liu thn thin vi mi trng c kh nng ng dng rng ri
(lactic acid) (PLA) nht hin nay.

1 TNG QUAN ngun gc du m khng phn hy sinh hc.


1.1 Gii thiu chung Nm 2002, cng ty Cargill Dow polymers
Polylactic acid (PLA) l mt trong nhng loi (LLC) a PLA vo sn xut qui m cng
biopolymers c s dng ph bin nht hin nay nghip u tin Nebraska vi cng sut 140.000
(khong 200.000 tn/nm) (Johansson, et al., 2012, tn/nm (Phuong, 2012). c tnh n nm 2015
Mehta, et al., 2005) do c bn ko cao, gi sn lng tiu th PLA c th t n 500.000
thnh thp, trong sut, kh nng tng hp sinh tn/nm v cn c th tng n 1 triu tn/nm n
hc cao. PLA c sn xut t tinh bt bp v y nm 2020 (Gongzhuling Annual Output, 2014).
l ngun nguyn liu c kh nng ti to t qu 1.2 Tnh cht ha l ca PLA
trnh sn xut nng nghip, khng nh cc loi
Poly (lactid acid) (PLA) c cng thc ha hc
polymer khc c sn xut t nguyn liu du
l (C3H4O2)n , Mw=0,89-2,98. 106 (Lu L, 1999,
m. c bit, PLA rt thn thin vi mi trng
Polylactic acid, 2014).
bi kh nng phn hy sinh hc cao (phn hy
hon ton t 90 n 180 ngy, ty theo iu kin PLA thuc nhm poly (-hydroxy ester), c
phn hy sinh hc) (Phuong, 2012). Chnh v vy, iu ch t ngun nguyn liu c ngun gc t
trong mi nm tr li y, PLA c tp trung nhin l tinh bt (a phn t tinh bt bp).
nghin cu v a vo s dng rng ri trn th
trng, thay th cho nhng sn phm polymers c PLA c tnh cht ha l gn ging nh poly

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Tap ch Khoa hoc Trng ai hoc C n Th Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

(ethylene terephtalat) (PET) c tng hp t kh nng phn hy sinh hc cao nn thn thin vi
nguyn liu ha thch nh cng cao, modun n mi trng (Drumright, et al., 2000, Sawyer,
hi cao, bn ko t ln, nhng khc vi cc 2003).
vt liu polymers c ngun gc du m l PLA c

Hnh 1: Cng thc cu to ca PLA (CAS: 26100-51-6)


Lu L, 1999, Polylactic acid, 2014
T hai loi ng phn ca Lactic acid trong phn trm ca PLLA trong hn hp blended s
Hnh 2 l D-Lactic, L-Lactic c th iu ch c nh hng n nhit chuyn thy tinh Tg v
ba dng ng phn hnh hc ca Lactide (Auras, et nhit nng chy Tm ca PLA thng mi
al., 2011), t thng qua phn ng polymer ha (Drumright, et al., 2000, Rasal, et al., 2010).
m vng, to ra ba dng PLA vi tnh cht ha l
c trnh by trong Bng 1: poly (D-Lactic acid)
(PDLA), poly (L-Lactic acid) (PLLA), poly (D,L-
Lactic acid) (PDLLA) (Drumright, et al., 2000,
Xiao, et al., 2012). Qu trnh to thnh Lactide l
mt trong nhng giai on quan trng nht bi
tinh khit quang hc ca Lactide c nh hng trc
tip n sn phm PLA. Trn th trng hin nay,
PLA thng mi l sn phm blend ca PLLA v
PDLLA c tng hp da trn phn ng Hnh 2: Hai dng ng phn ca monomer
polymers ha gia DLLA v LLA (Cargill/ Nature Lactic acid tng hp PLA
Works LLC Press Release, 2009). Trong t l Gupta, et al., 2007, Xiao, et al., 2012
Bng 1: Tnh cht ha l c bn ca 3 dng PLA (Xiao, et al., 2012)
Tnh cht PDLA PLLA PDLLA
Khng tan trong nc, tan tt trong cc dung mi hu c nh
Kh nng ha tan
benzene, chloroform, acetonitrile, tetrahydrofuran (THF), dioxane
Cu trc tinh th Kt tinh Bn kt tinh V nh hnh
Nhit nng chy (Tm) (oC) ~180 ~180 C th thay i
Nhit chuyn thy tinh(Tg) (oC) 50 60 55-60 C th thay i
Nhit phn hy (oC) ~200 ~200 185-200
dn di (%) < 10 C th thay i
Thi gian bn hy 370C trong dung
46 4-6 2 3
dch nc mui thng (thng)
1.3 Phng php chnh iu ch PLA 1.3.1 Phng php polymers ha trc tip
PLA c th c tng hp t ba phng php PLA ch yu c tng hp bng phng php
khc nhau nhng ch yu bng phng php polymer ha Lactic acid thnh PLA c khi lng
polymers ha trc tip v phng php cationic phn t thp (vi nghn n vi chc nghn vC)
ring opening polymersization (ROP) (Hartmann, sau tng phn t khi bng cc tc nhn ko di
et al., 1998, Linnemann, et al., 2003, Xiao, et al., mch cho n khi lng phn t mong mun.
2012). Phng trnh polymer ha bng phng php
polymer ha trc tip c th hin trong Hnh 3
(Garlotta, 2001, Xiao, et al., 2012).

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Tap ch Khoa hoc Trng ai hoc C n Th Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

Hnh 3: Phng trnh iu ch PLA bng phng php polymer ha trc tip (Xiao, et al., 2012)
1.3.2 Phng php m vng cationic ring (Sn(Oct)2) v mt s cht xc tc hu c nh 4-
opening polymersization (ROP) (dimethylamino)pyridine (DMAP), N-Heterocylic
carbene (NHC) (Linnemann, et al., 2003) lm xc
Phn ng to Lactide tri qua hai giai on.
tc trong dung dch alcohol iu kin nhit
u tin, monome Lactic acid c trng ngng
cao v p sut thp c trnh by Hnh 4.
to thnh oligome. Sau oligome tri qua qu
(Garlotta, 2001, Gupta, et al., 2007, Hartmann and
trnh polymer ha ng thi vng ha to thnh
Kaplan, 1998, Jimnez, et al., 2014, Nieuwenhuis,
Lactide. Phng php ROP s dng antimony,
1992).
zinc(II), titanium(IV), tin(II) 2-ethylhexanoate

Hnh 4: Phng php ROP iu ch PLA (Linnemann, et al., 2003, Xiao, et al., 2012)
1.4 u v nhc im ca PLA thp (Phuong, 2012), hn na PLA d b thy
1.4.1 u im phn, tc phn hy thp (Rasal, et al., 2010) v
sn xut PLA trong qui m cng nghip i hi
PLA l loi nha c kh nng phn hy sinh phi c chi ph cho quy trnh cng ngh cao, do
hc cao vi thi gian phn hy ngn, v vy c th gi thnh sn phm cao hn so vi cc loi nha c
tit kim c ngun nng lng nht nh x ngun gc ha thch nh PP, PE, PA,..( gi hin ti
l PLA. ng thi loi polymer ny c tng ca PLA trn th trng l 2,6-3,2 USD/kg, trong
thch sinh hc cao, khng c hi vi c th ngi, khi PP, PE ch c 1,2-1,8 USD/kg) (SE Asian,
nn c ng dng nhiu trong cc lnh vc c 2014).
bit l y sinh. Hin nay, PLA ang l sn phm
c sn xut v ng dng i tr trong cng 2 NG DNG CA PLA
nghip vi gi thnh r hn so vi cc loi nha Mc du polylactic acid c nhng u im ph
phn hy sinh hc khc (2-3,2 USD/kg) hp vi xu hng s dng vt liu polymers hin
(Information from NatureWorks LLC, 2014) vi nay, tuy nhin nhng yu im nh bn ko
bn ko v mun n hi cao (Tensile Strenght thp, kh nng chu nhit km, kh gia cng
55-75 MP, Youngs modulus 3-4GP) (Lu L, 1999, phn no hn ch kh nng ng dng PLA. Cng
PLA monomere (Polylactic Acid), 2014, Polylactic nh cc loi polymer khc trn th trng, PLA
Acid (PLA, 2014). thng c bin tnh trc khi a vo sn xut
1.4.2 Nhc im nhm p ng nhng yu cu c th trong tng
lnh vc ng dng. Cc nghin cu gn y cho
PLA c nhng hn ch v mt tnh cht nh:
thy PLA thng c bin tnh da trn hai
dn di (5-7%) (Information from NatureWorks
phng php. Phng php th nht l bin tnh b
LLC, 2014, Phuong, 2012), nhit chuyn thy
mt (surface modification) nhm to bm dnh
tinh thp Tg (60-68oC) dn n kh nng n nh
ca PLA vi vt liu khc. Vt liu bin tnh ny

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Tap ch Khoa hoc Trng ai hoc C n Th Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

c ng dng trong lnh vc y sinh (truyn dn biopolymers, c bit l PLA bin tnh l la chn
thuc). Phng php bin tnh th hai l trn hp tt nht trong lnh vc ny.
hoc ha do vi cc polymner khc nhm tng
V d: Trong s cc loi bin tnh, PLA/Poly
cng c tnh v kh nng chu nhit ca vt liu.
(Glycolic Acid) v copolymers
Phng php ny thng c ng dng trong lnh
poly (lactic acid-co-glycolic acid) (PLGA) l mt
vc bao b, ng gi, t, vt liu cch in v
trong s t polymers c Cc qun l thc phm
composites) (Gupta, et al., 2007, Jimnez, et al.,
v dc phm ca M (Food and Drug
2014, Obuchi, et al., 2011, Phuong, 2012).
Administration FDA) cho php ng dng lm sng
2.1.1 Trong k thut m ngi. Loi copolymers ny c th nghim
T nhng nm 1988, k thut cy m ra i v thnh cng trong vic ti to cc loi m nhiu
tr thnh phng php c ng dng ph bin c quan khc nhau nh: bng quang, sn, gan,
trong lnh vc y sinh (Drumright, et al., 2000). xng, van tim c hc (Ilan, et al., 2002).
Phng php ny gip ti to li cc m sng bng 2.1.2 Trong k thut dn truyn thuc
cch lin kt cc t bo sng vi h thng khung
Con ngi lun mong mun tm ra cch
bng cc vt liu sinh hc, cc t bo c th
phn phi cc dc cht vo ng c quan mong
sinh si ny n nhanh chng theo cc chiu hng
mun ti u ha kh nng iu tr ca n cng
khc nhau. Vt liu sinh hc ra i m ra con
nh duy tr cc hot tnh trong thi gian cn thit
ng tim nng trong vic thay th cc m sng
v gim thiu nhng tc dng ph ca thuc. Con
v c trong cy ghp ni tng. C rt nhiu loi vt
ngi th nghim lm sng nhiu nhm cht
liu sinh hc c a vo th nghim lm sng,
khc nhau trong vai tr cht dn truyn thuc nh:
trong c kim loi, v c nhng chng li c
liposome, cc ht nano lipid rn. Tuy nhin, trong
nhng nhc im ln nh tuy kim loi c c tnh
thi gian gn y cc loi polyester phn hy sinh
tt nhng li khng phn hy sinh hc, tch tr
hc trong c PLA, PGA v copolymers ca
trong c th con ngi gy nhng phn ng bt li
chng ( nh PLGA) c ng dng nhiu trong
(Mathew, et al., 2005), hay vt liu v c b hn
lnh vc truyn dn do vt liu c kh nng tng
ch do kh x l c v cu trc xp (Liu, et al.,
thch sinh hc cao, kh nng phn hy sinh hc,
2004). Vt liu sinh hc lm h thng khung trong
bn c hc, kh nng x l nhit v ha tan cao
phi tha cc iu kin sau: tng thch sinh
trong cc dung mi hu c. Bn cnh nhng u
hc cao, c c tnh thp, c kh nng phn hy
im trn th PLGA li c khuyt im l cu trc
sinh hc, vt liu phi c xp, c tnh v
ca chng li thiu i nhng nhm chc nng hot
kch thc ph hp, cc t bo hoc m c th
ha to iu kin tng tc vi cc t bo, v
tng trng v pht trin tt v loi b c cht
vy n lm cho hiu qu dn truyn thp v thi
c trong qu trnh trao i cht. Chnh v vy
gian lu trong c th khng lu.
Bng 2: ng dng ca mt s loi PLA bin tnh khc nhau trong k thut dn truyn thuc
(Drumright, et al., 2000)
Loi PLA ng dng Hiu qu
Tng cng vn chuyn qua nim
PLA- PEG dng ht Dn truyn cho bnh un vn
mc mi
H tr dn truyn cho thuc insulin xt Kim sot tt nng glucose
PLA-b-pluronic-b- PLA
ming cho bnh i tho ng loi 2 trong mu
Dn truyn cho nhm thuc paclitaxel
PLA microsphere Gim sng vim
chng ung th
Dn truyn cho nhm thuc 5 FU v Hon thnh qu trnh gii phng
PEO-PLA copolymers
paclitaxel thuc
PLA-PEG-PLA copolymers Dn truyn cho nhm thuc 5 FU v Kim sot tt qu trnh gii phng
paclitaxel thuc
AP-PEG-PLA Dn truyn thuc cho qu trnh iu tr C kh nng khng li cc t bo
ung th ung bu
V vy, gim thiu hn ch trn, cc nh siu nh, vi ht (MP) v ht nano (NP). Kt qu
nghin cu th nghim PLA bin tnh di th nghim cho thy, PLGA dng MP v NP l 2
nhiu dng bo ch khc nhau: bt vin, vin nang dng cho kt qu tt nht, v vi kch thc siu

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Tap ch Khoa hoc Trng ai hoc C n Th Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

nh, chng c th d dng thm thu qua cc mng trong cc siu th v cc vt gia dng khc nh ly,
t bo, ci thin kh nng dn truyn v vi c mung, a... c bit PLA bin tnh dng
tnh vt l ca ht nano, thi gian phn hy ca nanocomposites, c c tnh tng, tnh cht chn kh
PLGA gim ng k, duy tr c hot cht trong v chn quang cao so vi PLA thng thng. Bn
sut qu trnh vn chuyn (Drumright, et al., cnh , cc loi PLA bin tnh gia cng bng
2000). bentonite, c ph lp silicate v microcrystalline
cellusose c tnh khng tia UV v nh sng kh
Ngoi ra, PLA bin tnh cn c ng dng
kin (thnh phn c hi lm bin tnh cht lng
cy ghp hay ch to cc thit b y t nh thanh
sn phm ) nn thch hp ng dng lm bao b bo
nh hnh, tm, ghim, inh vt, ch t tiu
qun thc phm (Obuchi and Ogawa, 2011).
(Raghoebar, et al., 2006, Roney, et al., 2005)
hay ng dng PLA bin tnh cho phng php iu Ngoi ra trong bo qun thc phm, vic khng
tr cho da (nh teo m, so trn khun mt). khun lun c quan tm ch trng, bao b phi
2.2 ng dng trong lnh vc bao b ng gi p ng c yu cu v nhng thc phm ti
sng nh tht c, rau c qu, nu tip xc vi
So vi cc PLA thng thng vi nhng hn bao b nhim khun s sinh ra hot cht gy bnh.
ch nh gin, n nh nhit thp th PLA bin gii quyt vn , cc nh nghin cu tm
tnh khc phc c nhng khuyt im ca ra loi PLA bin tnh dng composite l hn hp
PLA thng thng. Theo cc nghin cu th PLA gia PLA dng nn lin kt vi ht pectin, trn b
bin tnh bng phng php ha do, copolymer mt vt liu s hp th v lu gi nhng hot
ha v composite c ng dng nhiu trong vic cht khng khun, hn ch qu trnh tn cng ca
sn xut mng phim mng ng gi thc phm, vi khun ln b mt tip xc gia bao b v
lm khay, hp ng thc n (Hnh 5), ti xch thc phm.

Hnh 5: ng dng ca PLA bin tnh trong sn phm bao b thc phm

2.2.1 ng dng trong lnh vc in t dummy card cm trc tip vo laptop chng bi
bn xm nhp vo. Nm 2006, n cn c ng
Nm 2002, cng ty Mitsubishi Plastics ch dng lm v in thoi cho dng sn phm cellular
to thnh cng PLA chu nhit bng k thut phun phone(Obuchi and Ogawa, 2011).
v n c a vo ng dng lm v my nghe
nhc Walkman ca cng ty Sony (Obuchi and Nm 2005, Fujitsu bt u ng dng composite
Ogawa, 2011). ca PLA vo thit b chng chy trong nh, sau
c cng ty NEC pht trin, s dng 10% si
PLA bin tnh dng composite c ng dng carbon gia cng, sn phm t c c tnh nng
v pht trin rng ri trong lnh vc in t. Nm gp 2 ln so vi s dng thp khng g truyn
2004, cng ty NEC Corp ca Nht s dng vt thng. Cng nm , Fujitsu cho ra i dng
liu composite nha nn PLA gia cng bng si my tnh xch tay FMV-BIBLO NB80K vi h
Kenaf (Vic thm si Kenaf gia cng gip tng thng khung c ch to t hn hp blend
cng kh nng chu nhit ca vt liu) lm PLA/PC/phosphorus (Obuchi and Ogawa, 2011).

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Tap ch Khoa hoc Trng ai hoc C n Th Phn A: Khoa hc T nhin, Cng ngh v Mi trng: 40 (2015): 43-49

Nm 2007, Samsung s dng hc vo sn xut qui m cng nghip vi tn


PLA/Polycarbonate bisphenol A (PC) trong vic gi Bio-Plex. Loi mng ph ny c th thay th
sn xut v cc linh kin in t ca mnh nh v cho loi mng bng Polyethylene (PE) truyn
in thoi, v my tnh,... (PC c Tg v kh nng thng. Ngoi ra, PLA bin tnh cn c ng dng
chu va p cao, v vy khi trn hp s nng kh lm chu cy, dy buc c chua v mt s vt dng
nng chu nhit v va p ca vt liu ) (Samsungs khc
Bioplastics for Automobile, 2014).
3 KT LUN
2.3 ng dng trong lnh vc t vn ti
Trong 10 nm tr li y, PLA pht trin
Hin nay, vt liu composites nn PLA l mt nhanh chng v dn c ch ng trong th trng
trong nhng vt liu c a chung v s dng vt liu polymers v ngy cng c cc nh sn
rng ri trong lnh vc t vn ti. Nm 2003, xut v ngi tiu dng la chn thay th cho cc
Cng ty Toyota ng dng composite nn PLA loi vt liu c ngun gc t du m. Tuy nhin,
v si kenaf sn xut ra lp xe d phng bng k nhng ng dng ca PLA bin tnh vn cn gp
thut c khun trong dng sn phm Raum v nhiu thch thc, tr ngi do mt s im yu v
Prius (Bioplastics, 2014). So vi lp xe thng mt c tnh (nh gin di thp) v cha tht s
thng, sn phm ch to t vt liu mi c kh ti u v mt k thut ln kinh t. Vic ci thin,
nng chu c tc ng bn ngoi cao hn. Bn nghin cu v pht trin rng nhng phng php
cnh , cng ty Toyota nghin cu vt liu bin tnh s mang li bc tin mi cho vic ng
xanh y tim nng cho cc b phn khc ca dng vt liu phn hy sinh hc PLA bin tnh vo
xe nh gh ngi, tm tri sn, tay cm (Bioplastics, trong i sng v cc ngnh cng nghip trong
2014). tng lai. Bn cnh , vic ng dng rng ri
Mt phng php khc c nghin cu l nha phn hy PLA bin tnh s gii quyt c
thm cht n ph hp vo nha nn PLA, kt hp phn no cc vn nhim mi trng gy ra do
vi k thut phun khun, cng ty Ford thnh cc loi vt liu polymers c ngun gc ha thch.
cng v ng dng composite nn PLA vo ch to TI LIU THAM KHO
h thng vm xe v tm thm tri cho dng sn
phm U (Auras, et al., 2011). Auras, R. A., L.-T. Lim, S. E. Selke and H.
Tsuji, 2011. Poly (lactic acid): synthesis,
Nm 2007, Mitsubishi ng dng PLA si v structures, properties, processing, and
Nylon 6 lm tm tri xe cho cc dng sn phm applications. John Wiley & Sons.
ca cng ty (Auras, et al., 2011).
Bioplastics, 2014.
Nm 2012, cng ty t Fiat- Italy, trong d n http://www.speautomotive.com. (ng nhp
Evolution, tin hnh nghin cu pht trin vt ngy 21/11/2014):
liu polymer xanh nhm thay cho cc b phn Cargill/ Nature Works LLC Press Release,
trong t m trc y c sn xut t cc loi 2009. http://www.natureworldsllc.com.
nha c ngun gc ha thch khc. Trong tng (ng nhp ngy 20/11/2014):
lai, composite nn PLA s c th thay th cho cc
Drumright, R. E., P. R. Gruber and D. E.
b phn khc ca cc dng xe Eco-friendly vi
Henton, 2000. Polylactic Acid Technology.
con ngi v mi trng (Project, 2014).
Advanced Materials: 1841-1846.
2.4 ng dng trong lnh vc nng nghip
Garlotta, D., 2001. A literature review of poly
Vic s dng mng ph gip tng tc chn (lactic acid). Journal of Polymers and the
ca cy trng, bo tn m v phn bn, c ch Environment: 63-84.
s tng trng ca c di, nhim nm v cn trng Gongzhuling Annual Output, 2014.
ph hoi. The FkuR Kunststoff GmbH, Willich hp http://www.english.jl.gov.cn (ng nhp
tc vi The Fraunhofer Institute UMSICHT, ngy 18/11/2014):
nghin cu thnh cng mng ph sinh hc t hn
Gupta, A. and V. Kumar, 2007. New emerging
hp blend ca PLA, cht ph gia v mt s
trends in synthetic biodegradable polymers
polymers phn hy sinh hc khc. Sn phm ny
PolyLactide: A critique. European polymer
c u im l kh nng phn hy chm hn cc
journal: 4053-4074.
loi mng ph sinh hc khc v kh nng chng
chu vi s thay i ca thi tit. V vy n nm
2005, Oerlemans Plastics a mng ph sinh

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Biopolymers from renewable resources. Phuong, V. T., 2012. Sustainable
Kaplan, DL, Ed: 367. Biocomposites from Renewable Ressources
Ilan, D. I. and A. L. Ladd, 2002. Bone graft and Recycled Polymers. PhD Thesis -
substitutes. Operative Techniques in Plastic University of Pisa:
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Jimnez, A., M. Peltzer and R. Ruseckaite, (ng nhp ngy 20/11/2014):
2014. Poly (lactic Acid) Science and Polylactic Acid (PLA, p., 2014.
Technology: Processing, Properties, http://www.makeitfrom.com/. (ng nhp
Additives and Applications. Royal Society ngy 22/11/2014):
of Chemistry. Project, E., 2014. http://evolutionproject.eu/
Johansson, C., J. Bras, I. Mondragon, P. (ng nhp ngy 20/11/2014):
Nechita, et al., 2012. Renewable fibers and Raghoebar, G. M., R. S. Liem, R. R. Bos, J. E.
bio-based materials for packaging Van Der Wal, et al., 2006. Resorbable screws
applicationsa review of recent for fixation of autologous bone grafts.
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