Research ArticleStudy on the Photodegradation Stability of Poly(butyleneSuccinate-co-butylene Adipate)TiO2 Nanocomposites

Lihai Cai Zhiguo Qi Jun Xu Baohua Guo and Zhongyao Huang

Key Laboratory of Advanced Materials of Ministry of Education Department of Chemical Engineering Tsinghua UniversityBeijing 100084 China

Correspondence should be addressed to Baohua Guo bhguomailtsinghuaeducn

Received 2 December 2018 Revised 17 January 2019 Accepted 29 January 2019 Published 3 March 2019

Academic Editor Leonardo Palmisano

Copyright copy 2019 Lihai Cai et al )is is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

A poly(butylene succinate-co-butylene adipate)TiO2 (PBSATiO2) nanocomposite was prepared by a melt-blending process )eeffect of TiO2 nanoparticles on the photodegradation behaviors of the nanocomposite was investigated by transmission electronmicroscopy (TEM) differential scanning calorimetry (DSC) Fourier-transform infrared spectroscopy (FT-IR) field-emissionscanning electron microscopy (FE-SEM) rheological measurements and mechanical tests TEM images of the PBSATiO2revealed that the TiO2 nanoparticles were well dispersed in the matrix without obvious aggregation )e FT-IR results indicatedthat the TiO2 nanoparticles can block high-energy ultraviolet (UV) light and reduce the degradation of the PBSA matrix )eviscosity analysis results indicated that the TiO2 nanoparticles inhibited the chain scission of PBSA matrix under irradiation Inaddition the surface of the PBSATiO2 films and their mechanical properties change less than that of untreated PBSA films duringthe photoaging process )e obtained results imply that the TiO2 nanoparticles can be considered as an efficientphotodegradation-resistant additive to PBSA for reducing photodegradation

1 Introduction

Biodegradable polymers have gained significant attentionbecause of their potential to alleviate certain environmentalproblems [1 2] Specifically poly(butylene succinate) (PBS)and copolymer poly(butylene succinate-co-butylene adi-pate) (PBSA) are very attractive for their mechanicalproperties and service temperatures which are even com-parable with current polyolefin materials [2] At presentthese chemicals can find applications in packaging materialsbiodegradable fibers injection-molded products mulchfilms and other areas [3 4] Unfortunately an insufficientservice life limits this materialrsquos further applications as it iseasy to become fragile during storage transportation andoutdoor use by exposure to heat oxygen and ultraviolet(UV) light [5] As reported by Konstantinou and Albanis [6]the service environment is the cause of oxidation and loss orbreakage of small molecular components which eventuallyleads to the poor physical properties of PBSA

As the stability of the mechanical properties during theaging process is important for extending service life many

researchers have attempted to reduce any change in thephysical properties of PBS over time such as chemicalcopolymerization physical blending and nano-compounding [2 7ndash9] However there is little research onimproving the stability of PBSArsquos mechanical propertiesduring the photoaging process

Yang et al [10] used SiO2 Al2O3 and ZnOnanoparticles asinhibitors on linear low-density polyethylene (LLDPE) andcompared three kinds of composites to the pure LLDPE afterirradiation )e results showed that all three types of nano-particles improved the photodegradation stability of theresulting nanocomposites Huang et al [11] prepared PBSTiO2nanocomposites via a vane extruder and found that the in-troduction of TiO2 improved the thermal stability and me-chanical properties stability of the nanocomposites Yang et al[12] studied the UV-blocking property of TiO2 powders withdifferent-sized additives for films and fabrics showing thatTiO2 is a goodUV-barrier-additive for polymermatrices due totheir properties of UV absorption scattering and reflection

In the studies mentioned [10ndash19] the TiO2 nano-additives have attracted a high degree of attention mainly

HindawiJournal of ChemistryVolume 2019 Article ID 5036019 9 pageshttpsdoiorg10115520195036019

because they are not only UV-screening agents but alsoperformance-enhancing additives Furthermore as TiO2 ismore refractive than that of most light-colored inorganicadditives such as SiO2 Al2O3 ZnO and others the ability ofshielding UV radiation is stronger than that of other ad-ditives [20]

)e purpose of this paper was to improve the pho-todegradation stability and prolong the service life ofPBSA by adding nano-TiO2 additives based on their UV-screening characteristics )e different TiO2 loadings ofPBSATiO2 nanocomposites were prepared by a melt-blending process )e effect of the TiO2 nanoparticleson the photodegradation behaviors of the nanocompositewas investigated by transmission electron microscopy(TEM) differential scanning calorimetry (DSC) Fourier-transform infrared spectroscopy (FT-IR) scanning elec-tron microscopy (SEM) rheological measurements andmechanical tests

2 Experimental

21Materials )ePBSA pellets were supplied by Blue RidgeTunhe Polyester Co Ltd (China) )e comonomer contentof the adipic acid used for PBSAwas set at 5mol)e indexof the melt flow was 161 g per 10min )e melting tem-perature was 1119degC Rutile TiO2 nanoparticles coated withsilicon-aluminum composite compounds were supplied byHangzhou Wanjing New Material Co Ltd (China)

22 PBSATiO2 Nanocomposite Preparation )e PBSA-added nano-TiO2 (PBSATiO2) nanocomposites were pre-pared by melt compounding by an RS600 HAAKE mixer)e speed of the rotary was 40ndash60 rpm and the mixingtemperature was 140degC When preparing the PBSATiO2nanocomposite with 01 wt TiO2 4995 g of PBSA pelletswas first fed into a mixing chamber and blended for 2min at140degC )en 005 g of TiO2 nanoparticles were added to thechamber and blended for another 10min PBSATiO2nanocomposites containing 05 10 and 15 wt TiO2 wereprepared according to the proportional relation )e purePBSA pellets were also blended in the mixing chamber for2min at 140degC )e films and plates of the pure PBSA andPBSATiO2 nanocomposites were molded by hot-pressing)e thicknesses of the film samples and plate samples wereabout 100 μm and 2mm respectively

23 Photoaging Test )e film and plate samples with dif-ferent TiO2 contents were exposed to the aging chamber foraccelerated photoaging tests )e aging test of the sampleswas carried out at 38plusmn 2degC in a Q-SUN xenon test chamber(Xe-3-HS Q-Lab Co USA) for different times )e energydistribution in the test chamber simulated that of the solarspectrum and the relative humidity in the chamber was30plusmn 5

24 Morphology Characterization )e surface morphologyof film samples was observed by SEM (JSM-7401 Japan)

)e SEM samples were plated with platinum before ob-servation at a scan voltage of 3 kV )e dispersion of TiO2nanoparticles in the PBSA matrix was observed by TEM(JEOL JEM-2000) at a voltage of 120 kV )e TEM sampleswere prepared with a microtome (Leica EMUC 6 Ger-many) at minus80degC and the samples were placed on coppergrids

25 Carbonyl IndexDetermination )e FT-IR spectra of thefilm samples were analyzed by an FT-IR spectrometer(Nicolet-6700 USA) with a Ge-attenuated total reflectiondetector )e wavenumber range was from 400 to 4000 cmminus1by signal averaging 32 scans at a resolution of 4 cmminus1 )ecarbonyl index (ACOACndashH) was defined as the area ratio ofcarbonyl absorbance to the reference peak [21ndash23] and thechanges in the carbonyl absorbance are represented in detailin the region of 1600ndash1800 cmminus1 )e 2856 cmminus1 peak wasattributed to the CndashH stretching according to the previousliterature [24]

26 Viscosity Aging Index Determination )e dynamicrheology of the plate samples was measured by a stress-strain-controlled rheometer (Anton Paar MCR301) [25 26])e diameter of the rheometer parallel plate was 25mm andthe testing gap was 1mm )e oscillatory shear model wasused in the rheological tests with parameters set at a tem-perature of 140degC a deformation strain of 1 and a sweepfrequency range from 001 to 100Hz In order to comparethe decrease of the zero-shear viscosity of samples afterirritation the viscosity aging index (VAI) was introducedaccording to the following formula

VAI ηlowast0

11138681113868111386811138681113868111386811138681113868minus ηlowastt

11138681113868111386811138681113868111386811138681113868

ηlowast01113868111386811138681113868

1113868111386811138681113868times 100 (1)

where |ηlowast0 | is the initial viscosity value with the data readfrom the curves of complex viscosity at 001Hz of samplesand |ηlowastt | is the aged viscosity value

27 7ermal Analysis )e thermal behavior of the filmsamples was tested by a differential thermal analyzer (Shi-madzu DSC-60 Japan) at an N2 flow of 50mLmin )esamples (3ndash5mg) were sealed in aluminum crucibles with anempty aluminum seal crucible as a reference During the testthe sample was heated from 30 to 160degC then held for 5minin order to eliminate the thermal history in the aging testthen the sample was cooled to 30degC )e rate of the heatingand cooling operations was both 10degCmin )e crystallinityof PBSATiO2 and pure PBSA nanocomposites was calcu-lated with the following formula

XC ΔHm

(1minusω)ΔH0m

times 100 (2)

where ΔHm is the melting enthalpy of the sample ΔH0m is

the melting enthalpy of PBS that is 100 crystalline(ΔH0

m 1103 Jg [27]) and ω is the content of TiO2 in thePBSA matrix by weight percentage

2 Journal of Chemistry

28 Mechanical Tests )e mechanical properties of the filmsamples were measured at 25plusmn 2degC by a TS-2000 tester(Gotech Inc Taiwan) including tensile strength andelongation at break )e sample was conditioned in 30relative humidity for 48 h at 25plusmn 2degC before testing )erising speed of the crosshead was 10mmmin )e final testresults were calculated from the mean value of five mea-surements for each sample

3 Results and Discussion

31 Dispersion of Nanoparticles in Polymer MatrixFigure 1 shows a TEM image of PBSATiO2 nanocompositescontaining 15 wt TiO2 from which it can be seen that theTiO2 nanoparticles are dispersed evenly in the PBSA matrixwithout obvious aggregation and the size of nanoparticles isfrom 30 to 50 nm )e good dispersion of TiO2 in PBSA canbe attributed to the surface modification by the coatedcompound [28] and the high sheer forces during extrusionwhich reduced the aggregation of the nanoparticles

32 FT-IR Characterization )e FT-IR spectra of purePBSA was acquired the peak in the 1046 cmminus1 region is dueto the stretching of the carbon-oxygen bond [29] )e1157 cmminus1 peak was assigned to the stretching of the carbon-oxygen-carbon group in the ester bond of PBSA [30] )eband region from 1650 to 1750 cmminus1 results from COstretching of the ester group [29] and the degradationfragments [31])e 2856 and 2946 cmminus1 peaks were assignedto CndashH stretching and the peak at 2856 cmminus1 peak was usedas the reference in calculating the value of the carbonyl index[24]

Carroccio [32] investigated the photo-oxidation ofpoly(butylene succinate) by mass spectrometry and ascer-tained three photo-oxidation processes of aliphatic poly-esters including α-hydrogen abstraction the Norrish I ofchain cleavage and the hydroxyl end groups oxidationDuring the processes of photo-oxidation many aldehydeand carboxyl groups were produced and the content ofcarboxyl groups changed dynamically at different oxidationtimes (Scheme 1) which corresponds with the increase andbroadening of CO peaks with increasing irradiation asseen in Figure 2 After further comparisons of the FT-IRcurves for the PBSATiO2 nanocomposite with pure PBSAunder the same irradiation time in Figure 2 the increase ofthe CO peak intensity for the PBSATiO2 nanocomposite isless than that of pure PBSA which indicates that the TiO2nanoparticles can significantly prevent the PBSA photo-degradation process

Normally the carboxyl groups can be used as a signatureto reveal the degree of photodegradation of PBSA [31]Figure 3 shows the changes in the carbonyl index of thePBSATiO2 nanocomposites and pure PBSA at differentirradiation times It can be seen that the photodegradationprocess starts immediately as the irradiation process starts[27])e carbonyl index of the pure PBSA is higher than thatof any PBSATiO2 nanocomposite With the increase of theTiO2 content the value of the carbonyl index decreases

gradually at the same irradiation time )is means that TiO2is an effective stabilizer for PBSA under irradiation )eimprovement in the photostability of PBSA with the nano-TiO2 results from the fact that the rutile-type TiO2 nano-particles have strong absorbability within the UV band bythe quantum size effect [11 12] which can block high-energy UV light effectively and reduce photodegradation ofthe PBSA matrix

33 Rheological Properties )e changes of molecular weightand the degradation degree of the polymer can be charac-terized by the change of viscosity [25 26] Figure 4 presentsthe complex viscosity of the PBSATiO2 nanocompositesand pure PBSA both before and after 360 h of irradiation Allsamples exhibit a non-Newtonian behavior in the entirefrequency range of the rheological test and show thecharacteristic of shear thinning )e zero-shear viscosities ofall nanocomposites are higher than that of pure PBSA whilethe complex viscosity (|ηlowast|) of all nanocomposites decreasesmore rapidly than that of pure PBSA with the increase offrequency demonstrating a much stronger shear thinningbehavior [24]

Figure 4(a) shows the complex viscosity (|ηlowast|) mea-sured at 140degC as a function of the frequency before irra-diation )e addition of nanoparticles leads to a significantincrease in the viscosity at low shear rates Similar behaviorshave been previously observed for other nanocomposites[33 34] with the reason behind the behavior being that TiO2can act as a physical entanglement point and improve thecomplex viscosity of PBSA at low frequencies)e formationof physical entanglement points in polymers results in thestress transfer between matrix and filler which is beneficialto the improvement of mechanical properties such as thetensile modulus and yield strength [34 35]

After irradiation it can be seen that there was an obviousreduction of the zero-shear viscosity in the samples after360 h of irradiation when compared to the initial samples(Figure 4(b)) As reported previously [36 37] there is apower law relationship between the molecular weight andthe zero-shear viscosity of linear polymers Correspondingto the Norrish I reaction of the photo-oxidation processes inScheme 1 the decrease of the zero-shear viscosity indicatesthat the photodegradation of PBSA provokes chain scissionthen the low-molecular-weight products have been formedby degradation [38] Table 1 lists the VAI values of purePBSA and the PBSATiO2 nanocomposites after 360 h ofirradiation )e VAI value of pure PBSA is as large as 893and the value decreases with the increase of TiO2 in thematrix of the PBSATiO2 nanocomposites which resultsfrom the positive effect of TiO2 during the photoagingprocess

34 7ermal Properties )e thermal properties of thesamples for different irradiation times were detected byDSC )e crystallization temperature (Tc) and meltingtemperature (Tm) were obtained by reading the peak valuesof cooling curves and heating curves respectively )ecrystallinity was calculated from the DSC curves

Journal of Chemistry 3

Figure 5 shows the change of Tc and crystallinity of thePBSATiO2 nanocomposites and pure PBSA both beforeirradiation and after being irradiated for 72 120 240 and360 h For the unaged samples it can be seen that the Tc andcrystallinity of pure PBSA are the smallest With the increaseof TiO2 content in the PBSATiO2 nanocomposites the Tcand crystallinity increase gradually )e relationship be-tween both the test parameters of the samples and the TiO2content shows that TiO2 is beneficial for promoting thenucleation and crystallization of PBSA which was also re-ported by Zhou et al [39]

From the data in Table 2 the Tm of all samples show fewdifferences after 360 h of irradiation However the Tc de-creases and the crystallinity increases significantly after360 h of irradiation Furthermore the pure PBSA showedthe largest decrease in Tc and the maximum increase incrystallinity )e decrease in Tc can be attributed to somelong chains of PBSA breaking during UV irradiation withthe broken short chains having stronger mobility which ishelpful for ordering shorter chains at lower temperature andreducing the crystallization temperature [23] In additionthe higher mobility of the broken molecules in the

O(CH2)3COOH

Hydroxyl endgroups oxidation

α-H abstraction

O(CH2)3COOH

O(CH2)4OCHO

OCOCH2CH3

COO(CH2)3CH3CO(CH2)2COOH

O(CH2)3COOH

COCH2COOH

HOCH2CH2CH2CH2OndashCOCH2CH2COndashOCHCH2CH2CH2OndashCO CH2CH2

Norrish IH

Scheme 1 Overall photo-oxidation processes in PBS and its copolymers [32]

Figure 1 TEM image of PBSA containing 15 wt TiO2 at a magnification of 50 kX

1800 1750 1700 1650 160000

01

02

03

04

05

06

07

08

Wavenumber (cmndash1)

0h72h120h

240h360h

Abso

rban

ce

(a)

1800 1750 1700 1650 160000

01

02

03

04

05

06

07

08

Wavenumber (cmndash1)

Abso

rban

ce

0h72h120h

240h360h

(b)

Figure 2 FT-IR spectra of (a) pure PBSA and (b) PBSATiO2 nanocomposites containing 15 wt TiO2 at different irradiation times

4 Journal of Chemistry

amorphous regions can cause them to rearrange and re-crystallize which promotes the increase of crystallinity [40]As the TiO2 content increases in pure PBSA the degradationof the PBSA chains decreases gradually and the effect of the

degraded shorter chains on reducing the crystallizationtemperature and promoting crystallization is weakenedaccordingly

35 SurfaceMorphology )emorphological changes causedby irradiation were analyzed by SEM to reveal the effect ofsurface changes on the photodegradation Figure 6 shows thesurface changes of PBSATiO2 nanocomposites and purePBSA film both before and after 360 h of irradiation at amagnification of 3 kX Before irradiation both the PBSATiO2 nanocomposites and pure PBSA film exhibit a rela-tively smooth surface

)e surface of the pure PBSA film becomes roughwith randomly distributed pores appearing after 360 h of

0 50 100 150 200 250 300 350 400

100

120

140

160

180

200

Irradiation time (h)

Carb

onyl

inde

x (A

C=O

AndashC

H)

PBSA01 TiO205 TiO2

15 TiO2

10 TiO2

Figure 3 Changes in the carbonyl index of PBSATiO2 nanocomposites and pure PBSA at different irradiation times

10ndash2 10ndash1 100 101 102102

103

104

105

Com

plex

visc

osity

(Pamiddots

)

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

Com

plex

visc

osity

(Pamiddots

)

10ndash2 10ndash1 100 101 102102

103

104

105

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(b)

Figure 4 Complex viscosity of pure PBSA and PBSATiO2 nanocomposites (a) before and (b) after 360 h of UV irradiation as a function offrequency at 140degC

Table 1 VAI values of PBSATiO2 nanocomposites before andafter 360 h of UV irradiation

TiO2 () |ηlowast|0 h(Pa middot s) |ηlowast|360 h(Pa middot s) VAI ()

0 10300 1105 89301 20700 9200 55605 22900 11400 50210 25400 14470 43015 41500 25430 387

Journal of Chemistry 5

irradiation which is consistent with the observations byZhang et al [23] )e formation of the pores is due to thedegradation of the PBSA beginning from the film surfaceand then deteriorating in the depth dimension with irra-diation time In contrast the surface of the PBSATiO2 filmchanges little under the same irradiation conditions whichshows that the TiO2 nanoparticles can effectively delay theaging of the PBSA matrix

36 Mechanical Properties Figure 7 shows the mechanicalproperties of film samples for different irradiation times Forthe pure PBSA film the tensile strength is 166MPa theelongation at break is 431 and both mechanical param-eters obviously decreased with the increase of irradiationtime For the unaged samples containing TiO2 nanoparticlesthe tensile strength increased and the elongation decreasedcompared to pure PBSA (Figure 7(a)) As the irradiationtime increased the elongation of PBSATiO2 nano-composites decreased gradually and the strength changedslowly As can be seen from Figure 7(b) as the aging timeincreases the elongation at break of the pure PBSA decreases

from 420 to 250 while that of nanocomposites con-taining 15 TiO2 decreases from 337 to 302 )echanging trend of elongation at break after irradiation issimilar to that of VAI in the rheological test in Table 1 whichindicates that nano-TiO2 can effectively prevent the breakingof molecular chains as the elongation at break has corre-lation with molecular weight and it has a positive effect onmaintaining the mechanical properties during irradiation

4 Conclusion

In this study rutile TiO2 nanoparticles were mixed withPBSA and the PBSATiO2 nanocomposites were successfullyprepared by melt-blending )e effect of the TiO2 nano-particles on the photodegradation behaviors of the nano-composites was investigated )e changes in the carbonylindex analysis thermal properties and rheological propertiesof the pure PBSA were caused by chain cleavage and groupoxidation under the photoaging process which spurred thesurface of the sample until it was rough and worsened itsmechanical properties )e rutile-type TiO2 nanoparticleswell dispersed in the matrix can retard the chain scission of

0 100 200 300 40065

70

75

80

85

90

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

zatio

n te

mpe

ratu

re (deg

C)

Irradiation time (h)

(a)

0 100 200 300 40040

45

50

55

60

65

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

nity

()

Irradiation time (h)

(b)

Figure 5 (a) Crystallization temperature and (b) crystallinity of PBSATiO2 nanocomposites and pure PBSA as a function of irradiationtime

Table 2 )ermal parameters of PBSATiO2 nanocomposites with and without irradiation time

TiO2 () Irradiation time (h) Tm (degC) Tc (degC) Xc ()0 0 1115 775 44101 0 1113 787 45105 0 1116 803 45610 0 1114 815 45915 0 1115 834 4620 360 1117 709 59601 360 1115 754 51905 360 1117 765 51710 360 1114 766 50115 360 1117 779 492

6 Journal of Chemistry

PBSA which effectively improves the surface integrity andmechanical properties of the nanocomposites under irradi-ation)is studymay promote the application of PBSA in theindustry and improve its service life

Data Availability

)e compressed data named DATArar used to support thefindings of this study have been deposited in the Figshare

(a) (b)

(c) (d)

Figure 6 SEM images of surface changes before UV irradiation of (a) pure PBSA and (b) PBSA containing 15 wt TiO2 and after 360 h UVirradiation of (c) pure PBSA and (d) PBSA containing 15 wt TiO2 at a magnification of 3 kX

0 100 200 300 4000

5

10

15

20

25

Tens

ile st

reng

th (M

Pa)

Irradiation time (h)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

0 100 200 300 400200

300

400

500

10 TiO215 TiO2

Elon

gatio

n at

bre

ak (

)

Irradiation time (h)

PBSA01 TiO205 TiO2

(b)

Figure 7 (a) Tensile strength and (b) elongation at the break of PBSATiO2 and pure PBSA films as a function of irradiation time

Journal of Chemistry 7

repository and the link is httpsfigsharecomsb00ca17289a252f90acd

Conflicts of Interest

)e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

)e authors thank the National Natural Science Foundationof China (Grant nos 51673110 and 51473085) the JointFunds of the National Natural Science Foundation of China(Grant no U1862205) and the Tsinghua University-SuzhouInnovation Leading Program (Grant no 20172140200) forthe financial support in this work

References

[1] M M Reddy S Vivekanandhan M Misra S K Bhatia andA K Mohanty ldquoBiobased plastics and bionanocompositescurrent status and future opportunitiesrdquo Progress in PolymerScience vol 38 no 10ndash12 pp 1653ndash1689 2013

[2] J Xu and B-H Guo ldquoPoly(butylene succinate) and its co-polymers research development and industrializationrdquoBiotechnology Journal vol 5 no 11 pp 1149ndash1163 2010

[3] S S Ray M Bousmina and K Okamoto ldquoStructure andproperties of nanocomposites based on poly(butylenesuccinate-co-adipate) and organically modified montmoril-loniterdquo Macromolecular Materials and Engineering vol 290no 8 pp 759ndash768 2005

[4] J A Ratto P J Stenhouse M Auerbach J Mitchell andR Farrell ldquoProcessing performance and biodegradability of athermoplastic aliphatic polyesterstarch systemrdquo Polymervol 40 no 24 pp 6777ndash6788 1999

[5] H Zhang J Yu H Wang and L Xue ldquoInvestigation ofmicrostructures and ultraviolet aging properties of organo-montmorilloniteSBS modified bitumenrdquo Materials Chemis-try and Physics vol 129 no 3 pp 769ndash776 2011

[6] I K Konstantinou and T A Albanis ldquoTiO2-assisted pho-tocatalytic degradation of azo dyes in aqueous solution ki-netic and mechanistic investigationsrdquo Applied Catalysis BEnvironmental vol 49 no 1 pp 1ndash14 2004

[7] J Du Y Zheng and L Xu ldquoBiodegradable liquid crystallinearomaticaliphatic copolyesters Part I synthesis character-ization and hydrolytic degradation of poly(butylenesuccinate-co-butylene terephthaloyldioxy dibenzoates)rdquoPolymer Degradation and Stability vol 91 no 12 pp 3281ndash3288 2006

[8] H-S Kim G-X Chen H-J Jin and J-S Yoon ldquoIn situcopolymerization of butylene succinate with twice func-tionalized organoclay thermal stabilityrdquoColloids and SurfacesA Physicochemical and Engineering Aspects vol 313-314pp 56ndash59 2008

[9] S S Ray ldquoVisualisation of nanoclay dispersion in polymermatrix by high resolution electron microscopy combined withelectron tomographyrdquo Macromolecular Materials and Engi-neering vol 294 no 4 pp 281ndash286 2009

[10] R Yang Y Li and J Yu ldquoPhoto-stabilization of linear lowdensity polyethylene by inorganic nano-particlesrdquo PolymerDegradation and Stability vol 88 no 2 pp 168ndash174 2005

[11] J Huang X Lu N Zhang et al ldquoStudy on the properties ofnano-TiO2polybutylene succinate composites prepared by

vane extruderrdquo Polymer Composites vol 35 no 1pp 4360ndash4365 2014

[12] H Yang S Zhu and N Pan ldquoStudying the mechanisms oftitanium dioxide as ultraviolet-blocking additive for films andfabrics by an improved schemerdquo Journal of Applied PolymerScience vol 92 no 5 pp 3201ndash3210 2004

[13] H Zhao and R K Y Li ldquoA study on the photo-degradation ofzinc oxide (ZnO) filled polypropylene nanocompositesrdquoPolymer vol 47 no 9 pp 3207ndash3217 2006

[14] O H Lin H M Akil and S Mahmud ldquoEffect of particlemorphology on the properties of polypropylenenanometriczinc oxide compositesrdquo Advanced Composites Letters vol 18no 3 pp 77ndash83 2009

[15] S Chandramouleeswaran S T Mhaske A A KatheP V Varadarajan V Prasad and N VigneshwaranldquoFunctional behaviour of polypropyleneZnO-soluble starchnanocompositesrdquo Nanotechnology vol 18 no 3 p 3857022007

[16] J He W Shao L Zhang C Deng and C Li ldquoCrystalli-zation behavior and UV-protection property of PET-ZnOnanocomposites prepared byin situpolymerizationrdquo Jour-nal of Applied Polymer Science vol 114 no 2 pp 1303ndash1311 2009

[17] M Miyauchi Y Li and H Shimizu ldquoEnhanced degradationin nanocomposites of TiO2 and biodegradable polymerrdquoEnvironmental Science amp Technology vol 42 no 12pp 4551ndash4554 2008

[18] Y Zhang M Chen and L Wu ldquoFabrication method ofTiO2ndashSiO2 hybrid capsules and their UV-protective prop-ertyrdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 353 no 2-3 2010

[19] R Manna S Nayak M Rahaman and D Khastgir ldquoEffect ofannealed titania on dielectric and mechanical properties ofethylene propylene diene monomer-titania nanocompositesrdquoE-Polymers vol 14 no 4 pp 267ndash275 2014

[20] T J Kemp and R A McIntyre ldquoMechanism of action oftitanium dioxide pigment in the photodegredation ofpoly(vinyl chloride) and other polymersrdquo Progress in ReactionKinetics and Mechanism vol 26 no 4 pp 337ndash374 2001

[21] L-H Cai Z-G Qi J Xu B-H Guo and Z-Y Huangldquo)ermo-oxidative degradation of nylon 1010 films colori-metric evaluation and its correlation with material proper-tiesrdquo Chinese Chemical Letters vol 28 no 5 pp 949ndash9542017

[22] T K N Nguyen H G Kim L K Kwac Q B BuiD M Nguyen and H Jeong ldquoTitanium dioxide-benzophenone hybrid as an effective catalyst for enhancedphotochemical degradation of low density polyethylenerdquo E-Polymers vol 18 no 6 pp 501ndash510 2018

[23] Y Zhang J Xu and B Guo ldquoPhotodegradation behavior ofpoly(butylene succinate-co-butylene adipate)ZnO nano-compositesrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 489 pp 173ndash181 2016

[24] Z Qi H Ye J Xu J Peng J Chen and B Guo ldquoSynthesis andcharacterizations of attapulgite reinforced branched poly(-butylene succinate) nanocompositesrdquo Colloids and SurfacesA Physicochemical and Engineering Aspects vol 436pp 26ndash33 2013

[25] S J Dalsin M A Hillmyer and F S Bates ldquoMolecular weightdependence of zero-shear viscosity in atactic polypropylenebottlebrush polymersrdquo ACS Macro Letters vol 3 no 5pp 423ndash427 2014

[26] D Quemada ldquoAging rejuvenation and thixotropy in complexfluids Time-dependence of the viscosity at rest and under

8 Journal of Chemistry

28 Mechanical Tests )e mechanical properties of the filmsamples were measured at 25plusmn 2degC by a TS-2000 tester(Gotech Inc Taiwan) including tensile strength andelongation at break )e sample was conditioned in 30relative humidity for 48 h at 25plusmn 2degC before testing )erising speed of the crosshead was 10mmmin )e final testresults were calculated from the mean value of five mea-surements for each sample

3 Results and Discussion

31 Dispersion of Nanoparticles in Polymer MatrixFigure 1 shows a TEM image of PBSATiO2 nanocompositescontaining 15 wt TiO2 from which it can be seen that theTiO2 nanoparticles are dispersed evenly in the PBSA matrixwithout obvious aggregation and the size of nanoparticles isfrom 30 to 50 nm )e good dispersion of TiO2 in PBSA canbe attributed to the surface modification by the coatedcompound [28] and the high sheer forces during extrusionwhich reduced the aggregation of the nanoparticles

32 FT-IR Characterization )e FT-IR spectra of purePBSA was acquired the peak in the 1046 cmminus1 region is dueto the stretching of the carbon-oxygen bond [29] )e1157 cmminus1 peak was assigned to the stretching of the carbon-oxygen-carbon group in the ester bond of PBSA [30] )eband region from 1650 to 1750 cmminus1 results from COstretching of the ester group [29] and the degradationfragments [31])e 2856 and 2946 cmminus1 peaks were assignedto CndashH stretching and the peak at 2856 cmminus1 peak was usedas the reference in calculating the value of the carbonyl index[24]

Carroccio [32] investigated the photo-oxidation ofpoly(butylene succinate) by mass spectrometry and ascer-tained three photo-oxidation processes of aliphatic poly-esters including α-hydrogen abstraction the Norrish I ofchain cleavage and the hydroxyl end groups oxidationDuring the processes of photo-oxidation many aldehydeand carboxyl groups were produced and the content ofcarboxyl groups changed dynamically at different oxidationtimes (Scheme 1) which corresponds with the increase andbroadening of CO peaks with increasing irradiation asseen in Figure 2 After further comparisons of the FT-IRcurves for the PBSATiO2 nanocomposite with pure PBSAunder the same irradiation time in Figure 2 the increase ofthe CO peak intensity for the PBSATiO2 nanocomposite isless than that of pure PBSA which indicates that the TiO2nanoparticles can significantly prevent the PBSA photo-degradation process

Normally the carboxyl groups can be used as a signatureto reveal the degree of photodegradation of PBSA [31]Figure 3 shows the changes in the carbonyl index of thePBSATiO2 nanocomposites and pure PBSA at differentirradiation times It can be seen that the photodegradationprocess starts immediately as the irradiation process starts[27])e carbonyl index of the pure PBSA is higher than thatof any PBSATiO2 nanocomposite With the increase of theTiO2 content the value of the carbonyl index decreases

gradually at the same irradiation time )is means that TiO2is an effective stabilizer for PBSA under irradiation )eimprovement in the photostability of PBSA with the nano-TiO2 results from the fact that the rutile-type TiO2 nano-particles have strong absorbability within the UV band bythe quantum size effect [11 12] which can block high-energy UV light effectively and reduce photodegradation ofthe PBSA matrix

33 Rheological Properties )e changes of molecular weightand the degradation degree of the polymer can be charac-terized by the change of viscosity [25 26] Figure 4 presentsthe complex viscosity of the PBSATiO2 nanocompositesand pure PBSA both before and after 360 h of irradiation Allsamples exhibit a non-Newtonian behavior in the entirefrequency range of the rheological test and show thecharacteristic of shear thinning )e zero-shear viscosities ofall nanocomposites are higher than that of pure PBSA whilethe complex viscosity (|ηlowast|) of all nanocomposites decreasesmore rapidly than that of pure PBSA with the increase offrequency demonstrating a much stronger shear thinningbehavior [24]

Figure 4(a) shows the complex viscosity (|ηlowast|) mea-sured at 140degC as a function of the frequency before irra-diation )e addition of nanoparticles leads to a significantincrease in the viscosity at low shear rates Similar behaviorshave been previously observed for other nanocomposites[33 34] with the reason behind the behavior being that TiO2can act as a physical entanglement point and improve thecomplex viscosity of PBSA at low frequencies)e formationof physical entanglement points in polymers results in thestress transfer between matrix and filler which is beneficialto the improvement of mechanical properties such as thetensile modulus and yield strength [34 35]

After irradiation it can be seen that there was an obviousreduction of the zero-shear viscosity in the samples after360 h of irradiation when compared to the initial samples(Figure 4(b)) As reported previously [36 37] there is apower law relationship between the molecular weight andthe zero-shear viscosity of linear polymers Correspondingto the Norrish I reaction of the photo-oxidation processes inScheme 1 the decrease of the zero-shear viscosity indicatesthat the photodegradation of PBSA provokes chain scissionthen the low-molecular-weight products have been formedby degradation [38] Table 1 lists the VAI values of purePBSA and the PBSATiO2 nanocomposites after 360 h ofirradiation )e VAI value of pure PBSA is as large as 893and the value decreases with the increase of TiO2 in thematrix of the PBSATiO2 nanocomposites which resultsfrom the positive effect of TiO2 during the photoagingprocess

34 7ermal Properties )e thermal properties of thesamples for different irradiation times were detected byDSC )e crystallization temperature (Tc) and meltingtemperature (Tm) were obtained by reading the peak valuesof cooling curves and heating curves respectively )ecrystallinity was calculated from the DSC curves

Journal of Chemistry 3

Figure 5 shows the change of Tc and crystallinity of thePBSATiO2 nanocomposites and pure PBSA both beforeirradiation and after being irradiated for 72 120 240 and360 h For the unaged samples it can be seen that the Tc andcrystallinity of pure PBSA are the smallest With the increaseof TiO2 content in the PBSATiO2 nanocomposites the Tcand crystallinity increase gradually )e relationship be-tween both the test parameters of the samples and the TiO2content shows that TiO2 is beneficial for promoting thenucleation and crystallization of PBSA which was also re-ported by Zhou et al [39]

From the data in Table 2 the Tm of all samples show fewdifferences after 360 h of irradiation However the Tc de-creases and the crystallinity increases significantly after360 h of irradiation Furthermore the pure PBSA showedthe largest decrease in Tc and the maximum increase incrystallinity )e decrease in Tc can be attributed to somelong chains of PBSA breaking during UV irradiation withthe broken short chains having stronger mobility which ishelpful for ordering shorter chains at lower temperature andreducing the crystallization temperature [23] In additionthe higher mobility of the broken molecules in the

O(CH2)3COOH

Hydroxyl endgroups oxidation

α-H abstraction

O(CH2)3COOH

O(CH2)4OCHO

OCOCH2CH3

COO(CH2)3CH3CO(CH2)2COOH

O(CH2)3COOH

COCH2COOH

HOCH2CH2CH2CH2OndashCOCH2CH2COndashOCHCH2CH2CH2OndashCO CH2CH2

Norrish IH

Scheme 1 Overall photo-oxidation processes in PBS and its copolymers [32]

Figure 1 TEM image of PBSA containing 15 wt TiO2 at a magnification of 50 kX

1800 1750 1700 1650 160000

01

02

03

04

05

06

07

08

Wavenumber (cmndash1)

0h72h120h

240h360h

Abso

rban

ce

(a)

1800 1750 1700 1650 160000

01

02

03

04

05

06

07

08

Wavenumber (cmndash1)

Abso

rban

ce

0h72h120h

240h360h

(b)

Figure 2 FT-IR spectra of (a) pure PBSA and (b) PBSATiO2 nanocomposites containing 15 wt TiO2 at different irradiation times

4 Journal of Chemistry

amorphous regions can cause them to rearrange and re-crystallize which promotes the increase of crystallinity [40]As the TiO2 content increases in pure PBSA the degradationof the PBSA chains decreases gradually and the effect of the

degraded shorter chains on reducing the crystallizationtemperature and promoting crystallization is weakenedaccordingly

35 SurfaceMorphology )emorphological changes causedby irradiation were analyzed by SEM to reveal the effect ofsurface changes on the photodegradation Figure 6 shows thesurface changes of PBSATiO2 nanocomposites and purePBSA film both before and after 360 h of irradiation at amagnification of 3 kX Before irradiation both the PBSATiO2 nanocomposites and pure PBSA film exhibit a rela-tively smooth surface

)e surface of the pure PBSA film becomes roughwith randomly distributed pores appearing after 360 h of

0 50 100 150 200 250 300 350 400

100

120

140

160

180

200

Irradiation time (h)

Carb

onyl

inde

x (A

C=O

AndashC

H)

PBSA01 TiO205 TiO2

15 TiO2

10 TiO2

Figure 3 Changes in the carbonyl index of PBSATiO2 nanocomposites and pure PBSA at different irradiation times

10ndash2 10ndash1 100 101 102102

103

104

105

Com

plex

visc

osity

(Pamiddots

)

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

Com

plex

visc

osity

(Pamiddots

)

10ndash2 10ndash1 100 101 102102

103

104

105

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(b)

Figure 4 Complex viscosity of pure PBSA and PBSATiO2 nanocomposites (a) before and (b) after 360 h of UV irradiation as a function offrequency at 140degC

Table 1 VAI values of PBSATiO2 nanocomposites before andafter 360 h of UV irradiation

TiO2 () |ηlowast|0 h(Pa middot s) |ηlowast|360 h(Pa middot s) VAI ()

0 10300 1105 89301 20700 9200 55605 22900 11400 50210 25400 14470 43015 41500 25430 387

Journal of Chemistry 5

irradiation which is consistent with the observations byZhang et al [23] )e formation of the pores is due to thedegradation of the PBSA beginning from the film surfaceand then deteriorating in the depth dimension with irra-diation time In contrast the surface of the PBSATiO2 filmchanges little under the same irradiation conditions whichshows that the TiO2 nanoparticles can effectively delay theaging of the PBSA matrix

36 Mechanical Properties Figure 7 shows the mechanicalproperties of film samples for different irradiation times Forthe pure PBSA film the tensile strength is 166MPa theelongation at break is 431 and both mechanical param-eters obviously decreased with the increase of irradiationtime For the unaged samples containing TiO2 nanoparticlesthe tensile strength increased and the elongation decreasedcompared to pure PBSA (Figure 7(a)) As the irradiationtime increased the elongation of PBSATiO2 nano-composites decreased gradually and the strength changedslowly As can be seen from Figure 7(b) as the aging timeincreases the elongation at break of the pure PBSA decreases

from 420 to 250 while that of nanocomposites con-taining 15 TiO2 decreases from 337 to 302 )echanging trend of elongation at break after irradiation issimilar to that of VAI in the rheological test in Table 1 whichindicates that nano-TiO2 can effectively prevent the breakingof molecular chains as the elongation at break has corre-lation with molecular weight and it has a positive effect onmaintaining the mechanical properties during irradiation

4 Conclusion

In this study rutile TiO2 nanoparticles were mixed withPBSA and the PBSATiO2 nanocomposites were successfullyprepared by melt-blending )e effect of the TiO2 nano-particles on the photodegradation behaviors of the nano-composites was investigated )e changes in the carbonylindex analysis thermal properties and rheological propertiesof the pure PBSA were caused by chain cleavage and groupoxidation under the photoaging process which spurred thesurface of the sample until it was rough and worsened itsmechanical properties )e rutile-type TiO2 nanoparticleswell dispersed in the matrix can retard the chain scission of

0 100 200 300 40065

70

75

80

85

90

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

zatio

n te

mpe

ratu

re (deg

C)

Irradiation time (h)

(a)

0 100 200 300 40040

45

50

55

60

65

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

nity

()

Irradiation time (h)

(b)

Figure 5 (a) Crystallization temperature and (b) crystallinity of PBSATiO2 nanocomposites and pure PBSA as a function of irradiationtime

Table 2 )ermal parameters of PBSATiO2 nanocomposites with and without irradiation time

TiO2 () Irradiation time (h) Tm (degC) Tc (degC) Xc ()0 0 1115 775 44101 0 1113 787 45105 0 1116 803 45610 0 1114 815 45915 0 1115 834 4620 360 1117 709 59601 360 1115 754 51905 360 1117 765 51710 360 1114 766 50115 360 1117 779 492

6 Journal of Chemistry

PBSA which effectively improves the surface integrity andmechanical properties of the nanocomposites under irradi-ation)is studymay promote the application of PBSA in theindustry and improve its service life

Data Availability

)e compressed data named DATArar used to support thefindings of this study have been deposited in the Figshare

(a) (b)

(c) (d)

Figure 6 SEM images of surface changes before UV irradiation of (a) pure PBSA and (b) PBSA containing 15 wt TiO2 and after 360 h UVirradiation of (c) pure PBSA and (d) PBSA containing 15 wt TiO2 at a magnification of 3 kX

0 100 200 300 4000

5

10

15

20

25

Tens

ile st

reng

th (M

Pa)

Irradiation time (h)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

0 100 200 300 400200

300

400

500

10 TiO215 TiO2

Elon

gatio

n at

bre

ak (

)

Irradiation time (h)

PBSA01 TiO205 TiO2

(b)

Figure 7 (a) Tensile strength and (b) elongation at the break of PBSATiO2 and pure PBSA films as a function of irradiation time

Journal of Chemistry 7

repository and the link is httpsfigsharecomsb00ca17289a252f90acd

Conflicts of Interest

)e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

)e authors thank the National Natural Science Foundationof China (Grant nos 51673110 and 51473085) the JointFunds of the National Natural Science Foundation of China(Grant no U1862205) and the Tsinghua University-SuzhouInnovation Leading Program (Grant no 20172140200) forthe financial support in this work

References

[1] M M Reddy S Vivekanandhan M Misra S K Bhatia andA K Mohanty ldquoBiobased plastics and bionanocompositescurrent status and future opportunitiesrdquo Progress in PolymerScience vol 38 no 10ndash12 pp 1653ndash1689 2013

[2] J Xu and B-H Guo ldquoPoly(butylene succinate) and its co-polymers research development and industrializationrdquoBiotechnology Journal vol 5 no 11 pp 1149ndash1163 2010

[3] S S Ray M Bousmina and K Okamoto ldquoStructure andproperties of nanocomposites based on poly(butylenesuccinate-co-adipate) and organically modified montmoril-loniterdquo Macromolecular Materials and Engineering vol 290no 8 pp 759ndash768 2005

[4] J A Ratto P J Stenhouse M Auerbach J Mitchell andR Farrell ldquoProcessing performance and biodegradability of athermoplastic aliphatic polyesterstarch systemrdquo Polymervol 40 no 24 pp 6777ndash6788 1999

[5] H Zhang J Yu H Wang and L Xue ldquoInvestigation ofmicrostructures and ultraviolet aging properties of organo-montmorilloniteSBS modified bitumenrdquo Materials Chemis-try and Physics vol 129 no 3 pp 769ndash776 2011

[6] I K Konstantinou and T A Albanis ldquoTiO2-assisted pho-tocatalytic degradation of azo dyes in aqueous solution ki-netic and mechanistic investigationsrdquo Applied Catalysis BEnvironmental vol 49 no 1 pp 1ndash14 2004

[7] J Du Y Zheng and L Xu ldquoBiodegradable liquid crystallinearomaticaliphatic copolyesters Part I synthesis character-ization and hydrolytic degradation of poly(butylenesuccinate-co-butylene terephthaloyldioxy dibenzoates)rdquoPolymer Degradation and Stability vol 91 no 12 pp 3281ndash3288 2006

[8] H-S Kim G-X Chen H-J Jin and J-S Yoon ldquoIn situcopolymerization of butylene succinate with twice func-tionalized organoclay thermal stabilityrdquoColloids and SurfacesA Physicochemical and Engineering Aspects vol 313-314pp 56ndash59 2008

[9] S S Ray ldquoVisualisation of nanoclay dispersion in polymermatrix by high resolution electron microscopy combined withelectron tomographyrdquo Macromolecular Materials and Engi-neering vol 294 no 4 pp 281ndash286 2009

[10] R Yang Y Li and J Yu ldquoPhoto-stabilization of linear lowdensity polyethylene by inorganic nano-particlesrdquo PolymerDegradation and Stability vol 88 no 2 pp 168ndash174 2005

[11] J Huang X Lu N Zhang et al ldquoStudy on the properties ofnano-TiO2polybutylene succinate composites prepared by

vane extruderrdquo Polymer Composites vol 35 no 1pp 4360ndash4365 2014

[12] H Yang S Zhu and N Pan ldquoStudying the mechanisms oftitanium dioxide as ultraviolet-blocking additive for films andfabrics by an improved schemerdquo Journal of Applied PolymerScience vol 92 no 5 pp 3201ndash3210 2004

[13] H Zhao and R K Y Li ldquoA study on the photo-degradation ofzinc oxide (ZnO) filled polypropylene nanocompositesrdquoPolymer vol 47 no 9 pp 3207ndash3217 2006

[14] O H Lin H M Akil and S Mahmud ldquoEffect of particlemorphology on the properties of polypropylenenanometriczinc oxide compositesrdquo Advanced Composites Letters vol 18no 3 pp 77ndash83 2009

[15] S Chandramouleeswaran S T Mhaske A A KatheP V Varadarajan V Prasad and N VigneshwaranldquoFunctional behaviour of polypropyleneZnO-soluble starchnanocompositesrdquo Nanotechnology vol 18 no 3 p 3857022007

[16] J He W Shao L Zhang C Deng and C Li ldquoCrystalli-zation behavior and UV-protection property of PET-ZnOnanocomposites prepared byin situpolymerizationrdquo Jour-nal of Applied Polymer Science vol 114 no 2 pp 1303ndash1311 2009

[17] M Miyauchi Y Li and H Shimizu ldquoEnhanced degradationin nanocomposites of TiO2 and biodegradable polymerrdquoEnvironmental Science amp Technology vol 42 no 12pp 4551ndash4554 2008

[18] Y Zhang M Chen and L Wu ldquoFabrication method ofTiO2ndashSiO2 hybrid capsules and their UV-protective prop-ertyrdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 353 no 2-3 2010

[19] R Manna S Nayak M Rahaman and D Khastgir ldquoEffect ofannealed titania on dielectric and mechanical properties ofethylene propylene diene monomer-titania nanocompositesrdquoE-Polymers vol 14 no 4 pp 267ndash275 2014

[20] T J Kemp and R A McIntyre ldquoMechanism of action oftitanium dioxide pigment in the photodegredation ofpoly(vinyl chloride) and other polymersrdquo Progress in ReactionKinetics and Mechanism vol 26 no 4 pp 337ndash374 2001

[21] L-H Cai Z-G Qi J Xu B-H Guo and Z-Y Huangldquo)ermo-oxidative degradation of nylon 1010 films colori-metric evaluation and its correlation with material proper-tiesrdquo Chinese Chemical Letters vol 28 no 5 pp 949ndash9542017

[22] T K N Nguyen H G Kim L K Kwac Q B BuiD M Nguyen and H Jeong ldquoTitanium dioxide-benzophenone hybrid as an effective catalyst for enhancedphotochemical degradation of low density polyethylenerdquo E-Polymers vol 18 no 6 pp 501ndash510 2018

[23] Y Zhang J Xu and B Guo ldquoPhotodegradation behavior ofpoly(butylene succinate-co-butylene adipate)ZnO nano-compositesrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 489 pp 173ndash181 2016

[24] Z Qi H Ye J Xu J Peng J Chen and B Guo ldquoSynthesis andcharacterizations of attapulgite reinforced branched poly(-butylene succinate) nanocompositesrdquo Colloids and SurfacesA Physicochemical and Engineering Aspects vol 436pp 26ndash33 2013

[25] S J Dalsin M A Hillmyer and F S Bates ldquoMolecular weightdependence of zero-shear viscosity in atactic polypropylenebottlebrush polymersrdquo ACS Macro Letters vol 3 no 5pp 423ndash427 2014

[26] D Quemada ldquoAging rejuvenation and thixotropy in complexfluids Time-dependence of the viscosity at rest and under

8 Journal of Chemistry

Figure 5 shows the change of Tc and crystallinity of thePBSATiO2 nanocomposites and pure PBSA both beforeirradiation and after being irradiated for 72 120 240 and360 h For the unaged samples it can be seen that the Tc andcrystallinity of pure PBSA are the smallest With the increaseof TiO2 content in the PBSATiO2 nanocomposites the Tcand crystallinity increase gradually )e relationship be-tween both the test parameters of the samples and the TiO2content shows that TiO2 is beneficial for promoting thenucleation and crystallization of PBSA which was also re-ported by Zhou et al [39]

From the data in Table 2 the Tm of all samples show fewdifferences after 360 h of irradiation However the Tc de-creases and the crystallinity increases significantly after360 h of irradiation Furthermore the pure PBSA showedthe largest decrease in Tc and the maximum increase incrystallinity )e decrease in Tc can be attributed to somelong chains of PBSA breaking during UV irradiation withthe broken short chains having stronger mobility which ishelpful for ordering shorter chains at lower temperature andreducing the crystallization temperature [23] In additionthe higher mobility of the broken molecules in the

O(CH2)3COOH

Hydroxyl endgroups oxidation

α-H abstraction

O(CH2)3COOH

O(CH2)4OCHO

OCOCH2CH3

COO(CH2)3CH3CO(CH2)2COOH

O(CH2)3COOH

COCH2COOH

HOCH2CH2CH2CH2OndashCOCH2CH2COndashOCHCH2CH2CH2OndashCO CH2CH2

Norrish IH

Scheme 1 Overall photo-oxidation processes in PBS and its copolymers [32]

Figure 1 TEM image of PBSA containing 15 wt TiO2 at a magnification of 50 kX

1800 1750 1700 1650 160000

01

02

03

04

05

06

07

08

Wavenumber (cmndash1)

0h72h120h

240h360h

Abso

rban

ce

(a)

1800 1750 1700 1650 160000

01

02

03

04

05

06

07

08

Wavenumber (cmndash1)

Abso

rban

ce

0h72h120h

240h360h

(b)

Figure 2 FT-IR spectra of (a) pure PBSA and (b) PBSATiO2 nanocomposites containing 15 wt TiO2 at different irradiation times

4 Journal of Chemistry

amorphous regions can cause them to rearrange and re-crystallize which promotes the increase of crystallinity [40]As the TiO2 content increases in pure PBSA the degradationof the PBSA chains decreases gradually and the effect of the

degraded shorter chains on reducing the crystallizationtemperature and promoting crystallization is weakenedaccordingly

35 SurfaceMorphology )emorphological changes causedby irradiation were analyzed by SEM to reveal the effect ofsurface changes on the photodegradation Figure 6 shows thesurface changes of PBSATiO2 nanocomposites and purePBSA film both before and after 360 h of irradiation at amagnification of 3 kX Before irradiation both the PBSATiO2 nanocomposites and pure PBSA film exhibit a rela-tively smooth surface

)e surface of the pure PBSA film becomes roughwith randomly distributed pores appearing after 360 h of

0 50 100 150 200 250 300 350 400

100

120

140

160

180

200

Irradiation time (h)

Carb

onyl

inde

x (A

C=O

AndashC

H)

PBSA01 TiO205 TiO2

15 TiO2

10 TiO2

Figure 3 Changes in the carbonyl index of PBSATiO2 nanocomposites and pure PBSA at different irradiation times

10ndash2 10ndash1 100 101 102102

103

104

105

Com

plex

visc

osity

(Pamiddots

)

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

Com

plex

visc

osity

(Pamiddots

)

10ndash2 10ndash1 100 101 102102

103

104

105

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(b)

Figure 4 Complex viscosity of pure PBSA and PBSATiO2 nanocomposites (a) before and (b) after 360 h of UV irradiation as a function offrequency at 140degC

Table 1 VAI values of PBSATiO2 nanocomposites before andafter 360 h of UV irradiation

TiO2 () |ηlowast|0 h(Pa middot s) |ηlowast|360 h(Pa middot s) VAI ()

0 10300 1105 89301 20700 9200 55605 22900 11400 50210 25400 14470 43015 41500 25430 387

Journal of Chemistry 5

irradiation which is consistent with the observations byZhang et al [23] )e formation of the pores is due to thedegradation of the PBSA beginning from the film surfaceand then deteriorating in the depth dimension with irra-diation time In contrast the surface of the PBSATiO2 filmchanges little under the same irradiation conditions whichshows that the TiO2 nanoparticles can effectively delay theaging of the PBSA matrix

36 Mechanical Properties Figure 7 shows the mechanicalproperties of film samples for different irradiation times Forthe pure PBSA film the tensile strength is 166MPa theelongation at break is 431 and both mechanical param-eters obviously decreased with the increase of irradiationtime For the unaged samples containing TiO2 nanoparticlesthe tensile strength increased and the elongation decreasedcompared to pure PBSA (Figure 7(a)) As the irradiationtime increased the elongation of PBSATiO2 nano-composites decreased gradually and the strength changedslowly As can be seen from Figure 7(b) as the aging timeincreases the elongation at break of the pure PBSA decreases

from 420 to 250 while that of nanocomposites con-taining 15 TiO2 decreases from 337 to 302 )echanging trend of elongation at break after irradiation issimilar to that of VAI in the rheological test in Table 1 whichindicates that nano-TiO2 can effectively prevent the breakingof molecular chains as the elongation at break has corre-lation with molecular weight and it has a positive effect onmaintaining the mechanical properties during irradiation

4 Conclusion

In this study rutile TiO2 nanoparticles were mixed withPBSA and the PBSATiO2 nanocomposites were successfullyprepared by melt-blending )e effect of the TiO2 nano-particles on the photodegradation behaviors of the nano-composites was investigated )e changes in the carbonylindex analysis thermal properties and rheological propertiesof the pure PBSA were caused by chain cleavage and groupoxidation under the photoaging process which spurred thesurface of the sample until it was rough and worsened itsmechanical properties )e rutile-type TiO2 nanoparticleswell dispersed in the matrix can retard the chain scission of

0 100 200 300 40065

70

75

80

85

90

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

zatio

n te

mpe

ratu

re (deg

C)

Irradiation time (h)

(a)

0 100 200 300 40040

45

50

55

60

65

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

nity

()

Irradiation time (h)

(b)

Figure 5 (a) Crystallization temperature and (b) crystallinity of PBSATiO2 nanocomposites and pure PBSA as a function of irradiationtime

Table 2 )ermal parameters of PBSATiO2 nanocomposites with and without irradiation time

TiO2 () Irradiation time (h) Tm (degC) Tc (degC) Xc ()0 0 1115 775 44101 0 1113 787 45105 0 1116 803 45610 0 1114 815 45915 0 1115 834 4620 360 1117 709 59601 360 1115 754 51905 360 1117 765 51710 360 1114 766 50115 360 1117 779 492

6 Journal of Chemistry

PBSA which effectively improves the surface integrity andmechanical properties of the nanocomposites under irradi-ation)is studymay promote the application of PBSA in theindustry and improve its service life

Data Availability

)e compressed data named DATArar used to support thefindings of this study have been deposited in the Figshare

(a) (b)

(c) (d)

Figure 6 SEM images of surface changes before UV irradiation of (a) pure PBSA and (b) PBSA containing 15 wt TiO2 and after 360 h UVirradiation of (c) pure PBSA and (d) PBSA containing 15 wt TiO2 at a magnification of 3 kX

0 100 200 300 4000

5

10

15

20

25

Tens

ile st

reng

th (M

Pa)

Irradiation time (h)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

0 100 200 300 400200

300

400

500

10 TiO215 TiO2

Elon

gatio

n at

bre

ak (

)

Irradiation time (h)

PBSA01 TiO205 TiO2

(b)

Figure 7 (a) Tensile strength and (b) elongation at the break of PBSATiO2 and pure PBSA films as a function of irradiation time

Journal of Chemistry 7

repository and the link is httpsfigsharecomsb00ca17289a252f90acd

Conflicts of Interest

)e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

)e authors thank the National Natural Science Foundationof China (Grant nos 51673110 and 51473085) the JointFunds of the National Natural Science Foundation of China(Grant no U1862205) and the Tsinghua University-SuzhouInnovation Leading Program (Grant no 20172140200) forthe financial support in this work

References

[1] M M Reddy S Vivekanandhan M Misra S K Bhatia andA K Mohanty ldquoBiobased plastics and bionanocompositescurrent status and future opportunitiesrdquo Progress in PolymerScience vol 38 no 10ndash12 pp 1653ndash1689 2013

[2] J Xu and B-H Guo ldquoPoly(butylene succinate) and its co-polymers research development and industrializationrdquoBiotechnology Journal vol 5 no 11 pp 1149ndash1163 2010

[3] S S Ray M Bousmina and K Okamoto ldquoStructure andproperties of nanocomposites based on poly(butylenesuccinate-co-adipate) and organically modified montmoril-loniterdquo Macromolecular Materials and Engineering vol 290no 8 pp 759ndash768 2005

[4] J A Ratto P J Stenhouse M Auerbach J Mitchell andR Farrell ldquoProcessing performance and biodegradability of athermoplastic aliphatic polyesterstarch systemrdquo Polymervol 40 no 24 pp 6777ndash6788 1999

[5] H Zhang J Yu H Wang and L Xue ldquoInvestigation ofmicrostructures and ultraviolet aging properties of organo-montmorilloniteSBS modified bitumenrdquo Materials Chemis-try and Physics vol 129 no 3 pp 769ndash776 2011

[6] I K Konstantinou and T A Albanis ldquoTiO2-assisted pho-tocatalytic degradation of azo dyes in aqueous solution ki-netic and mechanistic investigationsrdquo Applied Catalysis BEnvironmental vol 49 no 1 pp 1ndash14 2004

[7] J Du Y Zheng and L Xu ldquoBiodegradable liquid crystallinearomaticaliphatic copolyesters Part I synthesis character-ization and hydrolytic degradation of poly(butylenesuccinate-co-butylene terephthaloyldioxy dibenzoates)rdquoPolymer Degradation and Stability vol 91 no 12 pp 3281ndash3288 2006

[8] H-S Kim G-X Chen H-J Jin and J-S Yoon ldquoIn situcopolymerization of butylene succinate with twice func-tionalized organoclay thermal stabilityrdquoColloids and SurfacesA Physicochemical and Engineering Aspects vol 313-314pp 56ndash59 2008

[9] S S Ray ldquoVisualisation of nanoclay dispersion in polymermatrix by high resolution electron microscopy combined withelectron tomographyrdquo Macromolecular Materials and Engi-neering vol 294 no 4 pp 281ndash286 2009

[10] R Yang Y Li and J Yu ldquoPhoto-stabilization of linear lowdensity polyethylene by inorganic nano-particlesrdquo PolymerDegradation and Stability vol 88 no 2 pp 168ndash174 2005

[11] J Huang X Lu N Zhang et al ldquoStudy on the properties ofnano-TiO2polybutylene succinate composites prepared by

vane extruderrdquo Polymer Composites vol 35 no 1pp 4360ndash4365 2014

[12] H Yang S Zhu and N Pan ldquoStudying the mechanisms oftitanium dioxide as ultraviolet-blocking additive for films andfabrics by an improved schemerdquo Journal of Applied PolymerScience vol 92 no 5 pp 3201ndash3210 2004

[13] H Zhao and R K Y Li ldquoA study on the photo-degradation ofzinc oxide (ZnO) filled polypropylene nanocompositesrdquoPolymer vol 47 no 9 pp 3207ndash3217 2006

[14] O H Lin H M Akil and S Mahmud ldquoEffect of particlemorphology on the properties of polypropylenenanometriczinc oxide compositesrdquo Advanced Composites Letters vol 18no 3 pp 77ndash83 2009

[15] S Chandramouleeswaran S T Mhaske A A KatheP V Varadarajan V Prasad and N VigneshwaranldquoFunctional behaviour of polypropyleneZnO-soluble starchnanocompositesrdquo Nanotechnology vol 18 no 3 p 3857022007

[16] J He W Shao L Zhang C Deng and C Li ldquoCrystalli-zation behavior and UV-protection property of PET-ZnOnanocomposites prepared byin situpolymerizationrdquo Jour-nal of Applied Polymer Science vol 114 no 2 pp 1303ndash1311 2009

[17] M Miyauchi Y Li and H Shimizu ldquoEnhanced degradationin nanocomposites of TiO2 and biodegradable polymerrdquoEnvironmental Science amp Technology vol 42 no 12pp 4551ndash4554 2008

[18] Y Zhang M Chen and L Wu ldquoFabrication method ofTiO2ndashSiO2 hybrid capsules and their UV-protective prop-ertyrdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 353 no 2-3 2010

[19] R Manna S Nayak M Rahaman and D Khastgir ldquoEffect ofannealed titania on dielectric and mechanical properties ofethylene propylene diene monomer-titania nanocompositesrdquoE-Polymers vol 14 no 4 pp 267ndash275 2014

[20] T J Kemp and R A McIntyre ldquoMechanism of action oftitanium dioxide pigment in the photodegredation ofpoly(vinyl chloride) and other polymersrdquo Progress in ReactionKinetics and Mechanism vol 26 no 4 pp 337ndash374 2001

[21] L-H Cai Z-G Qi J Xu B-H Guo and Z-Y Huangldquo)ermo-oxidative degradation of nylon 1010 films colori-metric evaluation and its correlation with material proper-tiesrdquo Chinese Chemical Letters vol 28 no 5 pp 949ndash9542017

[22] T K N Nguyen H G Kim L K Kwac Q B BuiD M Nguyen and H Jeong ldquoTitanium dioxide-benzophenone hybrid as an effective catalyst for enhancedphotochemical degradation of low density polyethylenerdquo E-Polymers vol 18 no 6 pp 501ndash510 2018

[23] Y Zhang J Xu and B Guo ldquoPhotodegradation behavior ofpoly(butylene succinate-co-butylene adipate)ZnO nano-compositesrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 489 pp 173ndash181 2016

[24] Z Qi H Ye J Xu J Peng J Chen and B Guo ldquoSynthesis andcharacterizations of attapulgite reinforced branched poly(-butylene succinate) nanocompositesrdquo Colloids and SurfacesA Physicochemical and Engineering Aspects vol 436pp 26ndash33 2013

[25] S J Dalsin M A Hillmyer and F S Bates ldquoMolecular weightdependence of zero-shear viscosity in atactic polypropylenebottlebrush polymersrdquo ACS Macro Letters vol 3 no 5pp 423ndash427 2014

[26] D Quemada ldquoAging rejuvenation and thixotropy in complexfluids Time-dependence of the viscosity at rest and under

8 Journal of Chemistry

amorphous regions can cause them to rearrange and re-crystallize which promotes the increase of crystallinity [40]As the TiO2 content increases in pure PBSA the degradationof the PBSA chains decreases gradually and the effect of the

degraded shorter chains on reducing the crystallizationtemperature and promoting crystallization is weakenedaccordingly

35 SurfaceMorphology )emorphological changes causedby irradiation were analyzed by SEM to reveal the effect ofsurface changes on the photodegradation Figure 6 shows thesurface changes of PBSATiO2 nanocomposites and purePBSA film both before and after 360 h of irradiation at amagnification of 3 kX Before irradiation both the PBSATiO2 nanocomposites and pure PBSA film exhibit a rela-tively smooth surface

)e surface of the pure PBSA film becomes roughwith randomly distributed pores appearing after 360 h of

0 50 100 150 200 250 300 350 400

100

120

140

160

180

200

Irradiation time (h)

Carb

onyl

inde

x (A

C=O

AndashC

H)

PBSA01 TiO205 TiO2

15 TiO2

10 TiO2

Figure 3 Changes in the carbonyl index of PBSATiO2 nanocomposites and pure PBSA at different irradiation times

10ndash2 10ndash1 100 101 102102

103

104

105

Com

plex

visc

osity

(Pamiddots

)

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

Com

plex

visc

osity

(Pamiddots

)

10ndash2 10ndash1 100 101 102102

103

104

105

Frequency (Hz)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(b)

Figure 4 Complex viscosity of pure PBSA and PBSATiO2 nanocomposites (a) before and (b) after 360 h of UV irradiation as a function offrequency at 140degC

Table 1 VAI values of PBSATiO2 nanocomposites before andafter 360 h of UV irradiation

TiO2 () |ηlowast|0 h(Pa middot s) |ηlowast|360 h(Pa middot s) VAI ()

0 10300 1105 89301 20700 9200 55605 22900 11400 50210 25400 14470 43015 41500 25430 387

Journal of Chemistry 5

irradiation which is consistent with the observations byZhang et al [23] )e formation of the pores is due to thedegradation of the PBSA beginning from the film surfaceand then deteriorating in the depth dimension with irra-diation time In contrast the surface of the PBSATiO2 filmchanges little under the same irradiation conditions whichshows that the TiO2 nanoparticles can effectively delay theaging of the PBSA matrix

36 Mechanical Properties Figure 7 shows the mechanicalproperties of film samples for different irradiation times Forthe pure PBSA film the tensile strength is 166MPa theelongation at break is 431 and both mechanical param-eters obviously decreased with the increase of irradiationtime For the unaged samples containing TiO2 nanoparticlesthe tensile strength increased and the elongation decreasedcompared to pure PBSA (Figure 7(a)) As the irradiationtime increased the elongation of PBSATiO2 nano-composites decreased gradually and the strength changedslowly As can be seen from Figure 7(b) as the aging timeincreases the elongation at break of the pure PBSA decreases

from 420 to 250 while that of nanocomposites con-taining 15 TiO2 decreases from 337 to 302 )echanging trend of elongation at break after irradiation issimilar to that of VAI in the rheological test in Table 1 whichindicates that nano-TiO2 can effectively prevent the breakingof molecular chains as the elongation at break has corre-lation with molecular weight and it has a positive effect onmaintaining the mechanical properties during irradiation

4 Conclusion

In this study rutile TiO2 nanoparticles were mixed withPBSA and the PBSATiO2 nanocomposites were successfullyprepared by melt-blending )e effect of the TiO2 nano-particles on the photodegradation behaviors of the nano-composites was investigated )e changes in the carbonylindex analysis thermal properties and rheological propertiesof the pure PBSA were caused by chain cleavage and groupoxidation under the photoaging process which spurred thesurface of the sample until it was rough and worsened itsmechanical properties )e rutile-type TiO2 nanoparticleswell dispersed in the matrix can retard the chain scission of

0 100 200 300 40065

70

75

80

85

90

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

zatio

n te

mpe

ratu

re (deg

C)

Irradiation time (h)

(a)

0 100 200 300 40040

45

50

55

60

65

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

nity

()

Irradiation time (h)

(b)

Figure 5 (a) Crystallization temperature and (b) crystallinity of PBSATiO2 nanocomposites and pure PBSA as a function of irradiationtime

Table 2 )ermal parameters of PBSATiO2 nanocomposites with and without irradiation time

TiO2 () Irradiation time (h) Tm (degC) Tc (degC) Xc ()0 0 1115 775 44101 0 1113 787 45105 0 1116 803 45610 0 1114 815 45915 0 1115 834 4620 360 1117 709 59601 360 1115 754 51905 360 1117 765 51710 360 1114 766 50115 360 1117 779 492

6 Journal of Chemistry

PBSA which effectively improves the surface integrity andmechanical properties of the nanocomposites under irradi-ation)is studymay promote the application of PBSA in theindustry and improve its service life

Data Availability

)e compressed data named DATArar used to support thefindings of this study have been deposited in the Figshare

(a) (b)

(c) (d)

Figure 6 SEM images of surface changes before UV irradiation of (a) pure PBSA and (b) PBSA containing 15 wt TiO2 and after 360 h UVirradiation of (c) pure PBSA and (d) PBSA containing 15 wt TiO2 at a magnification of 3 kX

0 100 200 300 4000

5

10

15

20

25

Tens

ile st

reng

th (M

Pa)

Irradiation time (h)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

0 100 200 300 400200

300

400

500

10 TiO215 TiO2

Elon

gatio

n at

bre

ak (

)

Irradiation time (h)

PBSA01 TiO205 TiO2

(b)

Figure 7 (a) Tensile strength and (b) elongation at the break of PBSATiO2 and pure PBSA films as a function of irradiation time

Journal of Chemistry 7

repository and the link is httpsfigsharecomsb00ca17289a252f90acd

Conflicts of Interest

)e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

)e authors thank the National Natural Science Foundationof China (Grant nos 51673110 and 51473085) the JointFunds of the National Natural Science Foundation of China(Grant no U1862205) and the Tsinghua University-SuzhouInnovation Leading Program (Grant no 20172140200) forthe financial support in this work

References

[1] M M Reddy S Vivekanandhan M Misra S K Bhatia andA K Mohanty ldquoBiobased plastics and bionanocompositescurrent status and future opportunitiesrdquo Progress in PolymerScience vol 38 no 10ndash12 pp 1653ndash1689 2013

[2] J Xu and B-H Guo ldquoPoly(butylene succinate) and its co-polymers research development and industrializationrdquoBiotechnology Journal vol 5 no 11 pp 1149ndash1163 2010

[3] S S Ray M Bousmina and K Okamoto ldquoStructure andproperties of nanocomposites based on poly(butylenesuccinate-co-adipate) and organically modified montmoril-loniterdquo Macromolecular Materials and Engineering vol 290no 8 pp 759ndash768 2005

[4] J A Ratto P J Stenhouse M Auerbach J Mitchell andR Farrell ldquoProcessing performance and biodegradability of athermoplastic aliphatic polyesterstarch systemrdquo Polymervol 40 no 24 pp 6777ndash6788 1999

[5] H Zhang J Yu H Wang and L Xue ldquoInvestigation ofmicrostructures and ultraviolet aging properties of organo-montmorilloniteSBS modified bitumenrdquo Materials Chemis-try and Physics vol 129 no 3 pp 769ndash776 2011

[6] I K Konstantinou and T A Albanis ldquoTiO2-assisted pho-tocatalytic degradation of azo dyes in aqueous solution ki-netic and mechanistic investigationsrdquo Applied Catalysis BEnvironmental vol 49 no 1 pp 1ndash14 2004

[7] J Du Y Zheng and L Xu ldquoBiodegradable liquid crystallinearomaticaliphatic copolyesters Part I synthesis character-ization and hydrolytic degradation of poly(butylenesuccinate-co-butylene terephthaloyldioxy dibenzoates)rdquoPolymer Degradation and Stability vol 91 no 12 pp 3281ndash3288 2006

[8] H-S Kim G-X Chen H-J Jin and J-S Yoon ldquoIn situcopolymerization of butylene succinate with twice func-tionalized organoclay thermal stabilityrdquoColloids and SurfacesA Physicochemical and Engineering Aspects vol 313-314pp 56ndash59 2008

[9] S S Ray ldquoVisualisation of nanoclay dispersion in polymermatrix by high resolution electron microscopy combined withelectron tomographyrdquo Macromolecular Materials and Engi-neering vol 294 no 4 pp 281ndash286 2009

[10] R Yang Y Li and J Yu ldquoPhoto-stabilization of linear lowdensity polyethylene by inorganic nano-particlesrdquo PolymerDegradation and Stability vol 88 no 2 pp 168ndash174 2005

[11] J Huang X Lu N Zhang et al ldquoStudy on the properties ofnano-TiO2polybutylene succinate composites prepared by

vane extruderrdquo Polymer Composites vol 35 no 1pp 4360ndash4365 2014

[12] H Yang S Zhu and N Pan ldquoStudying the mechanisms oftitanium dioxide as ultraviolet-blocking additive for films andfabrics by an improved schemerdquo Journal of Applied PolymerScience vol 92 no 5 pp 3201ndash3210 2004

[13] H Zhao and R K Y Li ldquoA study on the photo-degradation ofzinc oxide (ZnO) filled polypropylene nanocompositesrdquoPolymer vol 47 no 9 pp 3207ndash3217 2006

[14] O H Lin H M Akil and S Mahmud ldquoEffect of particlemorphology on the properties of polypropylenenanometriczinc oxide compositesrdquo Advanced Composites Letters vol 18no 3 pp 77ndash83 2009

[15] S Chandramouleeswaran S T Mhaske A A KatheP V Varadarajan V Prasad and N VigneshwaranldquoFunctional behaviour of polypropyleneZnO-soluble starchnanocompositesrdquo Nanotechnology vol 18 no 3 p 3857022007

[16] J He W Shao L Zhang C Deng and C Li ldquoCrystalli-zation behavior and UV-protection property of PET-ZnOnanocomposites prepared byin situpolymerizationrdquo Jour-nal of Applied Polymer Science vol 114 no 2 pp 1303ndash1311 2009

[17] M Miyauchi Y Li and H Shimizu ldquoEnhanced degradationin nanocomposites of TiO2 and biodegradable polymerrdquoEnvironmental Science amp Technology vol 42 no 12pp 4551ndash4554 2008

[18] Y Zhang M Chen and L Wu ldquoFabrication method ofTiO2ndashSiO2 hybrid capsules and their UV-protective prop-ertyrdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 353 no 2-3 2010

[19] R Manna S Nayak M Rahaman and D Khastgir ldquoEffect ofannealed titania on dielectric and mechanical properties ofethylene propylene diene monomer-titania nanocompositesrdquoE-Polymers vol 14 no 4 pp 267ndash275 2014

[20] T J Kemp and R A McIntyre ldquoMechanism of action oftitanium dioxide pigment in the photodegredation ofpoly(vinyl chloride) and other polymersrdquo Progress in ReactionKinetics and Mechanism vol 26 no 4 pp 337ndash374 2001

[21] L-H Cai Z-G Qi J Xu B-H Guo and Z-Y Huangldquo)ermo-oxidative degradation of nylon 1010 films colori-metric evaluation and its correlation with material proper-tiesrdquo Chinese Chemical Letters vol 28 no 5 pp 949ndash9542017

[22] T K N Nguyen H G Kim L K Kwac Q B BuiD M Nguyen and H Jeong ldquoTitanium dioxide-benzophenone hybrid as an effective catalyst for enhancedphotochemical degradation of low density polyethylenerdquo E-Polymers vol 18 no 6 pp 501ndash510 2018

[23] Y Zhang J Xu and B Guo ldquoPhotodegradation behavior ofpoly(butylene succinate-co-butylene adipate)ZnO nano-compositesrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 489 pp 173ndash181 2016

[24] Z Qi H Ye J Xu J Peng J Chen and B Guo ldquoSynthesis andcharacterizations of attapulgite reinforced branched poly(-butylene succinate) nanocompositesrdquo Colloids and SurfacesA Physicochemical and Engineering Aspects vol 436pp 26ndash33 2013

[25] S J Dalsin M A Hillmyer and F S Bates ldquoMolecular weightdependence of zero-shear viscosity in atactic polypropylenebottlebrush polymersrdquo ACS Macro Letters vol 3 no 5pp 423ndash427 2014

[26] D Quemada ldquoAging rejuvenation and thixotropy in complexfluids Time-dependence of the viscosity at rest and under

8 Journal of Chemistry

irradiation which is consistent with the observations byZhang et al [23] )e formation of the pores is due to thedegradation of the PBSA beginning from the film surfaceand then deteriorating in the depth dimension with irra-diation time In contrast the surface of the PBSATiO2 filmchanges little under the same irradiation conditions whichshows that the TiO2 nanoparticles can effectively delay theaging of the PBSA matrix

36 Mechanical Properties Figure 7 shows the mechanicalproperties of film samples for different irradiation times Forthe pure PBSA film the tensile strength is 166MPa theelongation at break is 431 and both mechanical param-eters obviously decreased with the increase of irradiationtime For the unaged samples containing TiO2 nanoparticlesthe tensile strength increased and the elongation decreasedcompared to pure PBSA (Figure 7(a)) As the irradiationtime increased the elongation of PBSATiO2 nano-composites decreased gradually and the strength changedslowly As can be seen from Figure 7(b) as the aging timeincreases the elongation at break of the pure PBSA decreases

from 420 to 250 while that of nanocomposites con-taining 15 TiO2 decreases from 337 to 302 )echanging trend of elongation at break after irradiation issimilar to that of VAI in the rheological test in Table 1 whichindicates that nano-TiO2 can effectively prevent the breakingof molecular chains as the elongation at break has corre-lation with molecular weight and it has a positive effect onmaintaining the mechanical properties during irradiation

4 Conclusion

In this study rutile TiO2 nanoparticles were mixed withPBSA and the PBSATiO2 nanocomposites were successfullyprepared by melt-blending )e effect of the TiO2 nano-particles on the photodegradation behaviors of the nano-composites was investigated )e changes in the carbonylindex analysis thermal properties and rheological propertiesof the pure PBSA were caused by chain cleavage and groupoxidation under the photoaging process which spurred thesurface of the sample until it was rough and worsened itsmechanical properties )e rutile-type TiO2 nanoparticleswell dispersed in the matrix can retard the chain scission of

0 100 200 300 40065

70

75

80

85

90

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

zatio

n te

mpe

ratu

re (deg

C)

Irradiation time (h)

(a)

0 100 200 300 40040

45

50

55

60

65

10 TiO215 TiO2

PBSA01 TiO205 TiO2

Crys

talli

nity

()

Irradiation time (h)

(b)

Figure 5 (a) Crystallization temperature and (b) crystallinity of PBSATiO2 nanocomposites and pure PBSA as a function of irradiationtime

Table 2 )ermal parameters of PBSATiO2 nanocomposites with and without irradiation time

TiO2 () Irradiation time (h) Tm (degC) Tc (degC) Xc ()0 0 1115 775 44101 0 1113 787 45105 0 1116 803 45610 0 1114 815 45915 0 1115 834 4620 360 1117 709 59601 360 1115 754 51905 360 1117 765 51710 360 1114 766 50115 360 1117 779 492

6 Journal of Chemistry

PBSA which effectively improves the surface integrity andmechanical properties of the nanocomposites under irradi-ation)is studymay promote the application of PBSA in theindustry and improve its service life

Data Availability

)e compressed data named DATArar used to support thefindings of this study have been deposited in the Figshare

(a) (b)

(c) (d)

Figure 6 SEM images of surface changes before UV irradiation of (a) pure PBSA and (b) PBSA containing 15 wt TiO2 and after 360 h UVirradiation of (c) pure PBSA and (d) PBSA containing 15 wt TiO2 at a magnification of 3 kX

0 100 200 300 4000

5

10

15

20

25

Tens

ile st

reng

th (M

Pa)

Irradiation time (h)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

0 100 200 300 400200

300

400

500

10 TiO215 TiO2

Elon

gatio

n at

bre

ak (

)

Irradiation time (h)

PBSA01 TiO205 TiO2

(b)

Figure 7 (a) Tensile strength and (b) elongation at the break of PBSATiO2 and pure PBSA films as a function of irradiation time

Journal of Chemistry 7

repository and the link is httpsfigsharecomsb00ca17289a252f90acd

Conflicts of Interest

)e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

)e authors thank the National Natural Science Foundationof China (Grant nos 51673110 and 51473085) the JointFunds of the National Natural Science Foundation of China(Grant no U1862205) and the Tsinghua University-SuzhouInnovation Leading Program (Grant no 20172140200) forthe financial support in this work

References

[1] M M Reddy S Vivekanandhan M Misra S K Bhatia andA K Mohanty ldquoBiobased plastics and bionanocompositescurrent status and future opportunitiesrdquo Progress in PolymerScience vol 38 no 10ndash12 pp 1653ndash1689 2013

[2] J Xu and B-H Guo ldquoPoly(butylene succinate) and its co-polymers research development and industrializationrdquoBiotechnology Journal vol 5 no 11 pp 1149ndash1163 2010

[3] S S Ray M Bousmina and K Okamoto ldquoStructure andproperties of nanocomposites based on poly(butylenesuccinate-co-adipate) and organically modified montmoril-loniterdquo Macromolecular Materials and Engineering vol 290no 8 pp 759ndash768 2005

[4] J A Ratto P J Stenhouse M Auerbach J Mitchell andR Farrell ldquoProcessing performance and biodegradability of athermoplastic aliphatic polyesterstarch systemrdquo Polymervol 40 no 24 pp 6777ndash6788 1999

[5] H Zhang J Yu H Wang and L Xue ldquoInvestigation ofmicrostructures and ultraviolet aging properties of organo-montmorilloniteSBS modified bitumenrdquo Materials Chemis-try and Physics vol 129 no 3 pp 769ndash776 2011

[6] I K Konstantinou and T A Albanis ldquoTiO2-assisted pho-tocatalytic degradation of azo dyes in aqueous solution ki-netic and mechanistic investigationsrdquo Applied Catalysis BEnvironmental vol 49 no 1 pp 1ndash14 2004

[7] J Du Y Zheng and L Xu ldquoBiodegradable liquid crystallinearomaticaliphatic copolyesters Part I synthesis character-ization and hydrolytic degradation of poly(butylenesuccinate-co-butylene terephthaloyldioxy dibenzoates)rdquoPolymer Degradation and Stability vol 91 no 12 pp 3281ndash3288 2006

[8] H-S Kim G-X Chen H-J Jin and J-S Yoon ldquoIn situcopolymerization of butylene succinate with twice func-tionalized organoclay thermal stabilityrdquoColloids and SurfacesA Physicochemical and Engineering Aspects vol 313-314pp 56ndash59 2008

[9] S S Ray ldquoVisualisation of nanoclay dispersion in polymermatrix by high resolution electron microscopy combined withelectron tomographyrdquo Macromolecular Materials and Engi-neering vol 294 no 4 pp 281ndash286 2009

[10] R Yang Y Li and J Yu ldquoPhoto-stabilization of linear lowdensity polyethylene by inorganic nano-particlesrdquo PolymerDegradation and Stability vol 88 no 2 pp 168ndash174 2005

[11] J Huang X Lu N Zhang et al ldquoStudy on the properties ofnano-TiO2polybutylene succinate composites prepared by

vane extruderrdquo Polymer Composites vol 35 no 1pp 4360ndash4365 2014

[12] H Yang S Zhu and N Pan ldquoStudying the mechanisms oftitanium dioxide as ultraviolet-blocking additive for films andfabrics by an improved schemerdquo Journal of Applied PolymerScience vol 92 no 5 pp 3201ndash3210 2004

[13] H Zhao and R K Y Li ldquoA study on the photo-degradation ofzinc oxide (ZnO) filled polypropylene nanocompositesrdquoPolymer vol 47 no 9 pp 3207ndash3217 2006

[14] O H Lin H M Akil and S Mahmud ldquoEffect of particlemorphology on the properties of polypropylenenanometriczinc oxide compositesrdquo Advanced Composites Letters vol 18no 3 pp 77ndash83 2009

[15] S Chandramouleeswaran S T Mhaske A A KatheP V Varadarajan V Prasad and N VigneshwaranldquoFunctional behaviour of polypropyleneZnO-soluble starchnanocompositesrdquo Nanotechnology vol 18 no 3 p 3857022007

[16] J He W Shao L Zhang C Deng and C Li ldquoCrystalli-zation behavior and UV-protection property of PET-ZnOnanocomposites prepared byin situpolymerizationrdquo Jour-nal of Applied Polymer Science vol 114 no 2 pp 1303ndash1311 2009

[17] M Miyauchi Y Li and H Shimizu ldquoEnhanced degradationin nanocomposites of TiO2 and biodegradable polymerrdquoEnvironmental Science amp Technology vol 42 no 12pp 4551ndash4554 2008

[18] Y Zhang M Chen and L Wu ldquoFabrication method ofTiO2ndashSiO2 hybrid capsules and their UV-protective prop-ertyrdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 353 no 2-3 2010

[19] R Manna S Nayak M Rahaman and D Khastgir ldquoEffect ofannealed titania on dielectric and mechanical properties ofethylene propylene diene monomer-titania nanocompositesrdquoE-Polymers vol 14 no 4 pp 267ndash275 2014

[20] T J Kemp and R A McIntyre ldquoMechanism of action oftitanium dioxide pigment in the photodegredation ofpoly(vinyl chloride) and other polymersrdquo Progress in ReactionKinetics and Mechanism vol 26 no 4 pp 337ndash374 2001

[21] L-H Cai Z-G Qi J Xu B-H Guo and Z-Y Huangldquo)ermo-oxidative degradation of nylon 1010 films colori-metric evaluation and its correlation with material proper-tiesrdquo Chinese Chemical Letters vol 28 no 5 pp 949ndash9542017

[22] T K N Nguyen H G Kim L K Kwac Q B BuiD M Nguyen and H Jeong ldquoTitanium dioxide-benzophenone hybrid as an effective catalyst for enhancedphotochemical degradation of low density polyethylenerdquo E-Polymers vol 18 no 6 pp 501ndash510 2018

[23] Y Zhang J Xu and B Guo ldquoPhotodegradation behavior ofpoly(butylene succinate-co-butylene adipate)ZnO nano-compositesrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 489 pp 173ndash181 2016

[24] Z Qi H Ye J Xu J Peng J Chen and B Guo ldquoSynthesis andcharacterizations of attapulgite reinforced branched poly(-butylene succinate) nanocompositesrdquo Colloids and SurfacesA Physicochemical and Engineering Aspects vol 436pp 26ndash33 2013

[25] S J Dalsin M A Hillmyer and F S Bates ldquoMolecular weightdependence of zero-shear viscosity in atactic polypropylenebottlebrush polymersrdquo ACS Macro Letters vol 3 no 5pp 423ndash427 2014

[26] D Quemada ldquoAging rejuvenation and thixotropy in complexfluids Time-dependence of the viscosity at rest and under

8 Journal of Chemistry

PBSA which effectively improves the surface integrity andmechanical properties of the nanocomposites under irradi-ation)is studymay promote the application of PBSA in theindustry and improve its service life

Data Availability

)e compressed data named DATArar used to support thefindings of this study have been deposited in the Figshare

(a) (b)

(c) (d)

Figure 6 SEM images of surface changes before UV irradiation of (a) pure PBSA and (b) PBSA containing 15 wt TiO2 and after 360 h UVirradiation of (c) pure PBSA and (d) PBSA containing 15 wt TiO2 at a magnification of 3 kX

0 100 200 300 4000

5

10

15

20

25

Tens

ile st

reng

th (M

Pa)

Irradiation time (h)

PBSA01 TiO205 TiO2

10 TiO215 TiO2

(a)

0 100 200 300 400200

300

400

500

10 TiO215 TiO2

Elon

gatio

n at

bre

ak (

)

Irradiation time (h)

PBSA01 TiO205 TiO2

(b)

Figure 7 (a) Tensile strength and (b) elongation at the break of PBSATiO2 and pure PBSA films as a function of irradiation time

Journal of Chemistry 7

repository and the link is httpsfigsharecomsb00ca17289a252f90acd

Conflicts of Interest

)e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

)e authors thank the National Natural Science Foundationof China (Grant nos 51673110 and 51473085) the JointFunds of the National Natural Science Foundation of China(Grant no U1862205) and the Tsinghua University-SuzhouInnovation Leading Program (Grant no 20172140200) forthe financial support in this work

References

[1] M M Reddy S Vivekanandhan M Misra S K Bhatia andA K Mohanty ldquoBiobased plastics and bionanocompositescurrent status and future opportunitiesrdquo Progress in PolymerScience vol 38 no 10ndash12 pp 1653ndash1689 2013

[2] J Xu and B-H Guo ldquoPoly(butylene succinate) and its co-polymers research development and industrializationrdquoBiotechnology Journal vol 5 no 11 pp 1149ndash1163 2010

[3] S S Ray M Bousmina and K Okamoto ldquoStructure andproperties of nanocomposites based on poly(butylenesuccinate-co-adipate) and organically modified montmoril-loniterdquo Macromolecular Materials and Engineering vol 290no 8 pp 759ndash768 2005

[4] J A Ratto P J Stenhouse M Auerbach J Mitchell andR Farrell ldquoProcessing performance and biodegradability of athermoplastic aliphatic polyesterstarch systemrdquo Polymervol 40 no 24 pp 6777ndash6788 1999

[5] H Zhang J Yu H Wang and L Xue ldquoInvestigation ofmicrostructures and ultraviolet aging properties of organo-montmorilloniteSBS modified bitumenrdquo Materials Chemis-try and Physics vol 129 no 3 pp 769ndash776 2011

[6] I K Konstantinou and T A Albanis ldquoTiO2-assisted pho-tocatalytic degradation of azo dyes in aqueous solution ki-netic and mechanistic investigationsrdquo Applied Catalysis BEnvironmental vol 49 no 1 pp 1ndash14 2004

[7] J Du Y Zheng and L Xu ldquoBiodegradable liquid crystallinearomaticaliphatic copolyesters Part I synthesis character-ization and hydrolytic degradation of poly(butylenesuccinate-co-butylene terephthaloyldioxy dibenzoates)rdquoPolymer Degradation and Stability vol 91 no 12 pp 3281ndash3288 2006

[8] H-S Kim G-X Chen H-J Jin and J-S Yoon ldquoIn situcopolymerization of butylene succinate with twice func-tionalized organoclay thermal stabilityrdquoColloids and SurfacesA Physicochemical and Engineering Aspects vol 313-314pp 56ndash59 2008

[9] S S Ray ldquoVisualisation of nanoclay dispersion in polymermatrix by high resolution electron microscopy combined withelectron tomographyrdquo Macromolecular Materials and Engi-neering vol 294 no 4 pp 281ndash286 2009

[10] R Yang Y Li and J Yu ldquoPhoto-stabilization of linear lowdensity polyethylene by inorganic nano-particlesrdquo PolymerDegradation and Stability vol 88 no 2 pp 168ndash174 2005

[11] J Huang X Lu N Zhang et al ldquoStudy on the properties ofnano-TiO2polybutylene succinate composites prepared by

vane extruderrdquo Polymer Composites vol 35 no 1pp 4360ndash4365 2014

[12] H Yang S Zhu and N Pan ldquoStudying the mechanisms oftitanium dioxide as ultraviolet-blocking additive for films andfabrics by an improved schemerdquo Journal of Applied PolymerScience vol 92 no 5 pp 3201ndash3210 2004

[13] H Zhao and R K Y Li ldquoA study on the photo-degradation ofzinc oxide (ZnO) filled polypropylene nanocompositesrdquoPolymer vol 47 no 9 pp 3207ndash3217 2006

[14] O H Lin H M Akil and S Mahmud ldquoEffect of particlemorphology on the properties of polypropylenenanometriczinc oxide compositesrdquo Advanced Composites Letters vol 18no 3 pp 77ndash83 2009

[15] S Chandramouleeswaran S T Mhaske A A KatheP V Varadarajan V Prasad and N VigneshwaranldquoFunctional behaviour of polypropyleneZnO-soluble starchnanocompositesrdquo Nanotechnology vol 18 no 3 p 3857022007

[16] J He W Shao L Zhang C Deng and C Li ldquoCrystalli-zation behavior and UV-protection property of PET-ZnOnanocomposites prepared byin situpolymerizationrdquo Jour-nal of Applied Polymer Science vol 114 no 2 pp 1303ndash1311 2009

[17] M Miyauchi Y Li and H Shimizu ldquoEnhanced degradationin nanocomposites of TiO2 and biodegradable polymerrdquoEnvironmental Science amp Technology vol 42 no 12pp 4551ndash4554 2008

[18] Y Zhang M Chen and L Wu ldquoFabrication method ofTiO2ndashSiO2 hybrid capsules and their UV-protective prop-ertyrdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 353 no 2-3 2010

[19] R Manna S Nayak M Rahaman and D Khastgir ldquoEffect ofannealed titania on dielectric and mechanical properties ofethylene propylene diene monomer-titania nanocompositesrdquoE-Polymers vol 14 no 4 pp 267ndash275 2014

[20] T J Kemp and R A McIntyre ldquoMechanism of action oftitanium dioxide pigment in the photodegredation ofpoly(vinyl chloride) and other polymersrdquo Progress in ReactionKinetics and Mechanism vol 26 no 4 pp 337ndash374 2001

[21] L-H Cai Z-G Qi J Xu B-H Guo and Z-Y Huangldquo)ermo-oxidative degradation of nylon 1010 films colori-metric evaluation and its correlation with material proper-tiesrdquo Chinese Chemical Letters vol 28 no 5 pp 949ndash9542017

[22] T K N Nguyen H G Kim L K Kwac Q B BuiD M Nguyen and H Jeong ldquoTitanium dioxide-benzophenone hybrid as an effective catalyst for enhancedphotochemical degradation of low density polyethylenerdquo E-Polymers vol 18 no 6 pp 501ndash510 2018

[23] Y Zhang J Xu and B Guo ldquoPhotodegradation behavior ofpoly(butylene succinate-co-butylene adipate)ZnO nano-compositesrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 489 pp 173ndash181 2016

[24] Z Qi H Ye J Xu J Peng J Chen and B Guo ldquoSynthesis andcharacterizations of attapulgite reinforced branched poly(-butylene succinate) nanocompositesrdquo Colloids and SurfacesA Physicochemical and Engineering Aspects vol 436pp 26ndash33 2013

[25] S J Dalsin M A Hillmyer and F S Bates ldquoMolecular weightdependence of zero-shear viscosity in atactic polypropylenebottlebrush polymersrdquo ACS Macro Letters vol 3 no 5pp 423ndash427 2014

[26] D Quemada ldquoAging rejuvenation and thixotropy in complexfluids Time-dependence of the viscosity at rest and under

8 Journal of Chemistry

repository and the link is httpsfigsharecomsb00ca17289a252f90acd

Conflicts of Interest

)e authors declare that there are no conflicts of interestregarding the publication of this paper

Acknowledgments

)e authors thank the National Natural Science Foundationof China (Grant nos 51673110 and 51473085) the JointFunds of the National Natural Science Foundation of China(Grant no U1862205) and the Tsinghua University-SuzhouInnovation Leading Program (Grant no 20172140200) forthe financial support in this work

References

[1] M M Reddy S Vivekanandhan M Misra S K Bhatia andA K Mohanty ldquoBiobased plastics and bionanocompositescurrent status and future opportunitiesrdquo Progress in PolymerScience vol 38 no 10ndash12 pp 1653ndash1689 2013

[2] J Xu and B-H Guo ldquoPoly(butylene succinate) and its co-polymers research development and industrializationrdquoBiotechnology Journal vol 5 no 11 pp 1149ndash1163 2010

[3] S S Ray M Bousmina and K Okamoto ldquoStructure andproperties of nanocomposites based on poly(butylenesuccinate-co-adipate) and organically modified montmoril-loniterdquo Macromolecular Materials and Engineering vol 290no 8 pp 759ndash768 2005

[4] J A Ratto P J Stenhouse M Auerbach J Mitchell andR Farrell ldquoProcessing performance and biodegradability of athermoplastic aliphatic polyesterstarch systemrdquo Polymervol 40 no 24 pp 6777ndash6788 1999

[5] H Zhang J Yu H Wang and L Xue ldquoInvestigation ofmicrostructures and ultraviolet aging properties of organo-montmorilloniteSBS modified bitumenrdquo Materials Chemis-try and Physics vol 129 no 3 pp 769ndash776 2011

[6] I K Konstantinou and T A Albanis ldquoTiO2-assisted pho-tocatalytic degradation of azo dyes in aqueous solution ki-netic and mechanistic investigationsrdquo Applied Catalysis BEnvironmental vol 49 no 1 pp 1ndash14 2004

[7] J Du Y Zheng and L Xu ldquoBiodegradable liquid crystallinearomaticaliphatic copolyesters Part I synthesis character-ization and hydrolytic degradation of poly(butylenesuccinate-co-butylene terephthaloyldioxy dibenzoates)rdquoPolymer Degradation and Stability vol 91 no 12 pp 3281ndash3288 2006

[8] H-S Kim G-X Chen H-J Jin and J-S Yoon ldquoIn situcopolymerization of butylene succinate with twice func-tionalized organoclay thermal stabilityrdquoColloids and SurfacesA Physicochemical and Engineering Aspects vol 313-314pp 56ndash59 2008

[9] S S Ray ldquoVisualisation of nanoclay dispersion in polymermatrix by high resolution electron microscopy combined withelectron tomographyrdquo Macromolecular Materials and Engi-neering vol 294 no 4 pp 281ndash286 2009

[10] R Yang Y Li and J Yu ldquoPhoto-stabilization of linear lowdensity polyethylene by inorganic nano-particlesrdquo PolymerDegradation and Stability vol 88 no 2 pp 168ndash174 2005

[11] J Huang X Lu N Zhang et al ldquoStudy on the properties ofnano-TiO2polybutylene succinate composites prepared by

vane extruderrdquo Polymer Composites vol 35 no 1pp 4360ndash4365 2014

[12] H Yang S Zhu and N Pan ldquoStudying the mechanisms oftitanium dioxide as ultraviolet-blocking additive for films andfabrics by an improved schemerdquo Journal of Applied PolymerScience vol 92 no 5 pp 3201ndash3210 2004

[13] H Zhao and R K Y Li ldquoA study on the photo-degradation ofzinc oxide (ZnO) filled polypropylene nanocompositesrdquoPolymer vol 47 no 9 pp 3207ndash3217 2006

[14] O H Lin H M Akil and S Mahmud ldquoEffect of particlemorphology on the properties of polypropylenenanometriczinc oxide compositesrdquo Advanced Composites Letters vol 18no 3 pp 77ndash83 2009

[15] S Chandramouleeswaran S T Mhaske A A KatheP V Varadarajan V Prasad and N VigneshwaranldquoFunctional behaviour of polypropyleneZnO-soluble starchnanocompositesrdquo Nanotechnology vol 18 no 3 p 3857022007

[16] J He W Shao L Zhang C Deng and C Li ldquoCrystalli-zation behavior and UV-protection property of PET-ZnOnanocomposites prepared byin situpolymerizationrdquo Jour-nal of Applied Polymer Science vol 114 no 2 pp 1303ndash1311 2009

[17] M Miyauchi Y Li and H Shimizu ldquoEnhanced degradationin nanocomposites of TiO2 and biodegradable polymerrdquoEnvironmental Science amp Technology vol 42 no 12pp 4551ndash4554 2008

[18] Y Zhang M Chen and L Wu ldquoFabrication method ofTiO2ndashSiO2 hybrid capsules and their UV-protective prop-ertyrdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 353 no 2-3 2010

[19] R Manna S Nayak M Rahaman and D Khastgir ldquoEffect ofannealed titania on dielectric and mechanical properties ofethylene propylene diene monomer-titania nanocompositesrdquoE-Polymers vol 14 no 4 pp 267ndash275 2014

[20] T J Kemp and R A McIntyre ldquoMechanism of action oftitanium dioxide pigment in the photodegredation ofpoly(vinyl chloride) and other polymersrdquo Progress in ReactionKinetics and Mechanism vol 26 no 4 pp 337ndash374 2001

[21] L-H Cai Z-G Qi J Xu B-H Guo and Z-Y Huangldquo)ermo-oxidative degradation of nylon 1010 films colori-metric evaluation and its correlation with material proper-tiesrdquo Chinese Chemical Letters vol 28 no 5 pp 949ndash9542017

[22] T K N Nguyen H G Kim L K Kwac Q B BuiD M Nguyen and H Jeong ldquoTitanium dioxide-benzophenone hybrid as an effective catalyst for enhancedphotochemical degradation of low density polyethylenerdquo E-Polymers vol 18 no 6 pp 501ndash510 2018

[23] Y Zhang J Xu and B Guo ldquoPhotodegradation behavior ofpoly(butylene succinate-co-butylene adipate)ZnO nano-compositesrdquo Colloids and Surfaces A Physicochemical andEngineering Aspects vol 489 pp 173ndash181 2016

[24] Z Qi H Ye J Xu J Peng J Chen and B Guo ldquoSynthesis andcharacterizations of attapulgite reinforced branched poly(-butylene succinate) nanocompositesrdquo Colloids and SurfacesA Physicochemical and Engineering Aspects vol 436pp 26ndash33 2013

[25] S J Dalsin M A Hillmyer and F S Bates ldquoMolecular weightdependence of zero-shear viscosity in atactic polypropylenebottlebrush polymersrdquo ACS Macro Letters vol 3 no 5pp 423ndash427 2014

[26] D Quemada ldquoAging rejuvenation and thixotropy in complexfluids Time-dependence of the viscosity at rest and under

8 Journal of Chemistry

constant shear rate or shear stressrdquo Physics vol 18pp 129ndash137 2008

[27] M S Nikolic and J Djonlagic ldquoSynthesis and characterizationof biodegradable poly(butylene succinate-co-butylene adi-pate)srdquo Polymer Degradation and Stability vol 74 no 2pp 263ndash270 2001

[28] J Godnjavec J Zabret B Znoj S Skale N Veronovski andP Venturini ldquoInvestigation of surface modification of rutileTiO2 nanoparticles with SiO2Al2O3 on the properties ofpolyacrylic composite coatingrdquo Progress in Organic Coatingsvol 77 no 1 pp 47ndash52 2014

[29] H-S Kim H-J Kim J-W Lee and I-G Choi ldquoBio-degradability of bio-flour filled biodegradable poly(butylenesuccinate) bio-composites in natural and compost soilrdquoPolymer Degradation and Stability vol 91 no 5 pp 1117ndash1127 2006

[30] T Uesaka K Nakane S Maeda T Ogihara and N OgataldquoStructure and physical properties of poly(butylenesuccinate)cellulose acetate blendsrdquo Polymer vol 41 no 23pp 8449ndash8454 2000

[31] T Kijchavengkul R Auras M Rubino S Selke M Ngouajioand R T Fernandez ldquoBiodegradation and hydrolysis rate ofaliphatic aromatic polyesterrdquo Polymer Degradation and Sta-bility vol 95 no 12 pp 2641ndash2647 2010

[32] S Carroccio P Rizzarelli C Puglisi and G MontaudoldquoMALDI investigation of photooxidation in aliphatic poly-esters poly(butylene succinate)rdquo Macromolecules vol 37no 17 pp 6576ndash6586 2004

[33] H Eslami M Grmela and M Bousmina ldquoLinear andnonlinear rheology of polymerlayered silicate nano-compositesrdquo Journal of Rheology vol 54 no 3 pp 539ndash5622010

[34] S S Ray and M Bousmina ldquoPoly(butylene sucinate-co-adipate)montmorillonite nanocomposites effect of organicmodifier miscibility on structure properties and viscoelas-ticityrdquo Polymer vol 46 no 26 pp 12430ndash12439 2005

[35] J K Mishra K-J Hwang and C-S Ha ldquoPreparation me-chanical and rheological properties of a thermoplastic poly-olefin (TPO)organoclay nanocomposite with reference to theeffect of maleic anhydride modified polypropylene as acompatibilizerrdquo Polymer vol 46 no 6 pp 1995ndash2002 2005

[36] T G Fox Jr and P J Flory ldquoFurther studies on the meltviscosity of polyisobutylenerdquo Journal of Physical Chemistryvol 55 no 2 pp 221ndash234 1951

[37] R H Colby L J Fetters and W W Graessley ldquo)e meltviscosity-molecular weight relationship for linear polymersrdquoMacromolecules vol 20 no 9 pp 2226ndash2237 1987

[38] M Gardette S )erias J-L Gardette M Murariu andP Dubois ldquoPhotooxidation of polylactidecalcium sulphatecompositesrdquo Polymer Degradation and Stability vol 96 no 4pp 616ndash623 2011

[39] W Zhou T Xu X Wang et al ldquoIn situ polymerizednanocomposites of poly (butylene succinate)TiO2 nanofibersmolecular weight morphology and thermal propertiesrdquoJournal of Applied Polymer Science vol 127 no 1 pp 733ndash739 2012

[40] A Pegoretti and A Penati ldquoRecycled poly(ethylene tere-phthalate) and its short glass fibres composites effects ofhygrothermal aging on the thermo-mechanical behaviourrdquoPolymer vol 45 no 23 pp 7995ndash8004 2004

Journal of Chemistry 9

TribologyAdvances in

Hindawiwwwhindawicom Volume 2018

Hindawiwwwhindawicom Volume 2018

International Journal ofInternational Journal ofPhotoenergy

Hindawiwwwhindawicom Volume 2018

Journal of

Chemistry

Hindawiwwwhindawicom Volume 2018

Advances inPhysical Chemistry

Hindawiwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2018

Bioinorganic Chemistry and ApplicationsHindawiwwwhindawicom Volume 2018

SpectroscopyInternational Journal of

Hindawiwwwhindawicom Volume 2018

Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom

The Scientific World Journal

Volume 2018

Medicinal ChemistryInternational Journal of

Hindawiwwwhindawicom Volume 2018

NanotechnologyHindawiwwwhindawicom Volume 2018

Journal of

Applied ChemistryJournal of

Hindawiwwwhindawicom Volume 2018

Hindawiwwwhindawicom Volume 2018

Biochemistry Research International

Hindawiwwwhindawicom Volume 2018

Enzyme Research

Hindawiwwwhindawicom Volume 2018

Journal of

SpectroscopyAnalytical ChemistryInternational Journal of

Hindawiwwwhindawicom Volume 2018

MaterialsJournal of

Hindawiwwwhindawicom Volume 2018

Hindawiwwwhindawicom Volume 2018

BioMed Research International Electrochemistry

International Journal of

Hindawiwwwhindawicom Volume 2018

Na

nom

ate

ria

ls

Hindawiwwwhindawicom Volume 2018

Journal ofNanomaterials

Submit your manuscripts atwwwhindawicom

TribologyAdvances in

Hindawiwwwhindawicom Volume 2018

Hindawiwwwhindawicom Volume 2018

International Journal ofInternational Journal ofPhotoenergy

Hindawiwwwhindawicom Volume 2018

Journal of

Chemistry

Hindawiwwwhindawicom Volume 2018

Advances inPhysical Chemistry

Hindawiwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2018

Bioinorganic Chemistry and ApplicationsHindawiwwwhindawicom Volume 2018

SpectroscopyInternational Journal of

Hindawiwwwhindawicom Volume 2018

Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawiwwwhindawicom

The Scientific World Journal

Volume 2018

Medicinal ChemistryInternational Journal of

Hindawiwwwhindawicom Volume 2018

NanotechnologyHindawiwwwhindawicom Volume 2018

Journal of

Applied ChemistryJournal of

Hindawiwwwhindawicom Volume 2018

Hindawiwwwhindawicom Volume 2018

Biochemistry Research International

Hindawiwwwhindawicom Volume 2018

Enzyme Research

Hindawiwwwhindawicom Volume 2018

Journal of

SpectroscopyAnalytical ChemistryInternational Journal of

Hindawiwwwhindawicom Volume 2018

MaterialsJournal of

Hindawiwwwhindawicom Volume 2018

Hindawiwwwhindawicom Volume 2018

BioMed Research International Electrochemistry

International Journal of

Hindawiwwwhindawicom Volume 2018

Na

nom

ate

ria

ls

Hindawiwwwhindawicom Volume 2018

Journal ofNanomaterials

Submit your manuscripts atwwwhindawicom