Research ArticleInfluence of the Copper-Containing SBA-15 Silica Fillers onthe Mechanical Properties of High Density Polyethylene
Adam Gnatowski1 Jerzy Jelonkiewicz2 Aukasz Laskowski2 and Magdalena Laskowska2
1 Institute of Mechanical Technologies Czestochowa University of Technology Al Armii Krajowej 21 42-201 Czestochowa Poland2Institute of Computational Intelligence Unit of Microelectronics and Nanotechnology Czestochowa University of TechnologyAl Armii Krajowej 36 42-201 Czestochowa Poland
Correspondence should be addressed to Łukasz Laskowski lukaszlaskowskikikpczpl
Received 5 January 2016 Revised 18 April 2016 Accepted 21 April 2016
Academic Editor Pushpendra Kumar
Copyright copy 2016 Adam Gnatowski et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited
The paper concerns the mechanical properties of the high density polyethylene (HDPE) with the copper-containing SBA-15 silicafillerThe considered filler is the SBA-15mesoporous silica containing copper ions bounded inside channels via propyl-phosphonateanchoring groups With its help we can impart the biocidal properties to this plastic Research covered mechanical propertiesthermal analysis colour shine and nanomolecular structure Dynamical properties of the samples like modulus 1198641015840 changes andmechanical core loss angle tangent 119905119892120575 versus temperature and vibration frequency were tested using DMTA method Level ofcrystallinity was tested using DSC method while their structure was observed with going through light by optical microscopeHardness and toughness of obtained samples were also defined Colour and shine changes of the samples were observed for PE-HD with filler contents 05 and 1 Modulus value changes versus temperature and frequency were notified for the samples withmodifier There were no differences in modulus changes versus temperature for samples with and without filler and frequencies1 and 10Hz It was detected that melting enthalpy of the samples with the modifier decreases Moreover some influence of thesamples with filler on colour and shine was observed
1 Introduction
Functional materials have become very promising since 90sof XX century mainly due to their programmable propertiesAmong the functional materials significant are species basedon SBA-15mesoporous silica [1 2] which can find applicationas druggene delivery systems [3 4] biosensors [5] in sepa-ration recycling catalysis [6 7] or electronics [8 9] Silica-based nanomaterials can be used in their pure form as coatsor as plasticsrsquomodifiers Using thesematerials in this last formsignificantly extends their application area
The great example of functional material can be SBA-15mesoporous silica modified by copper ions anchored insidepores via propyl-phosphonate units [10] These species areconsidered in the paper As it is commonly known copper hasstrong biocidal properties [11] Such properties are enhancedwith decreasing dimensions of the copper grains To ourknowledge nowadays the smallest nanoparticles of copper
have at least 150 of atoms [12] but those used commerciallyhave over 100 times higher number of atoms in one grainIn our previous works [10 13] we have proposed limitingdispersion of copper inside material separate copper ions arehomogenously distributed inside silica matrix
The material containing copper ions dispersed in thesilica matrix has been investigated paying special attention toits antimicrobial properties [13] As it was shown thematerialreveals comparable biocidal properties as commercially usedsolution of nanocopper Additionally its advantage is that thecopper is bounded to silica matrix so when used for coatingthe heavy metals environment contamination is limitedAnother benefit of such a form is a possibility of using it assimple fillers for plastics For this implementation the SBA-15mesoporous silica containing anchoring copper ions appearsto be ideal Presumably adding this copper-containing mate-rial to selected plastics makes them biocidalThis property ofthe material will be tested later Modification process of
Hindawi Publishing CorporationJournal of NanomaterialsVolume 2016 Article ID 3291719 8 pageshttpdxdoiorg10115520163291719
2 Journal of Nanomaterials
plastics by adding fillers seems to be relatively simple it issufficient to add considered filler into the plastic duringmelt-ing process Nevertheless fillers can modify also mechanicalproperties of plastics which can transfer to their commercialuse constraints In the paper we present the influence ofthe copper-containing SBA-15 silica filler on the mechanicalproperties of the high density polyethylene (HDPE)
The features of modified material depend on structuralfactors of polymer as well as added modifier The struc-tural factors are mainly molecular weight macromolecularchemical structure physical layout of a chain crystallinityand molecular orientation while conditions of use are tem-perature load time pressure strain type and so on [14ndash19] Estimation of possible feature changes of these materi-als with added modifiers plays important role in polymermaterials composition Technical and economical usabilityof polymer materials depends on their required stiffnessand strength to fulfil durability condition Typically obtainedmechanical characteristics when material is statically loadedstretched compressed or twisted are not sufficient to pre-dict its behaviour in extreme condition of usage and longexploitation time Selection of research methods that enableprediction of material viscoelastic features change with thetime based on experimental data is still an open problemAs tested materials are viscoelastic all factors related totheir physicomechanical features deeply depend on time andtemperature So applied research methods must considerthese dependencies One of thesemethods is thermal analysisof mechanical features dynamics (DMTA) It is used tomeasure the relaxation modules versus time with constanttemperature and as a function of load change frequency andtemperature [16 19ndash22] Mechanical characteristics obtainedfor statical load at room temperature are not adequate to esti-mate materialrsquos features in any other conditions of usage [1619ndash22]The way to recognise all properties of tested materialsand estimate their behaviour in predicted usage conditionsis to obtain for them viscoelastic functions that contain allrequired thermal and time dependencies Sinusoidal wayof loading applied for tests is similar to load schemes inpracticeThermal analysis ofmechanical properties dynamics(DMTA) is one of the common schemes to evaluate changesin polymer materials for wide temperature range and loadfrequency variation As an effect of this analysis we getprocess of dynamic Young modules changes and mechanicalcore loss angle tangent modification Being familiar withthese dependencies allows us to find relationship betweenmolecular parameters and mechanical properties of polymermaterials [16 19ndash22] In the paper we presented the followingproperties of created materials mechanical dynamics ther-mal properties shine and structure
2 Materials and Methods
For test we used polyethylene Hostalen GC 7260 manu-factured by Lyondell and Basell with 05 and 1 fillerof mesoporous SBA-15 silica containing propyl-phosphonateunits activated by copper ions in the form of powder Thefiller was prepared according to the procedure described in[10] To obtain composite we mechanically stirred polymer
Oscillator Force
Displacementsensor
Adjustment withstepper motor
Force signal
DisplacementProbe
Displacementdevice
Sample holder
Sample
Control
Sample
Heatingcooling
signal
thermocouple
thermocouple
Figure 1 The scheme of the device for the three-point bending ofsample
withmodifier andmade it more flexible with a help of a screwextruder Then the material was granulated We applied thefollowing parameters of the composite extrusion
(i) Screw rotational speed 250mms(ii) Nozzle temperature 200∘C
The abovementioned procedure was applied for both PE-HD + 05 weight of modifier and PE-HD + 1 weight ofmodifier Samples were obtained on the extruder KRAUSSMAFFEI KM65-160C1 Applied extrusion parameters for allsamples were as follows maximal pressure in the plasticiserpart 60MPa extrusion time 06 s clamps pressure 30MPaclamps time 28 s cooling time 15 s dozing time 66 s formclosing force 650 kN form temperature minus40∘C and extrusiontemperature 195∘C
Dynamic mechanical properties were tested with a helpof DMA 242 device manufactured by Netzsch with three-point free bent grip handle of the beam sample as it wasdepicted in Figure 1 Applied bent frequency was 1 and 10Hzat temperature range of minus150ndash140∘C with heating ramp of2∘Cmin
On the basis of the force value and the sample strainincluding its size value of modulus 1198641015840 the loss module 11986410158401015840and mechanical core loss angle tangent 119905119892120575 were calculatedObtained results were presented in the form of diagrams ofthe abovementioned quantities versus temperature and vibra-tion frequencyThermal properties of the samples were testedusing DSC method while their structure was observed withgoing through light by optical microscope
TheDSC tests were made using scanning microcalorime-ter type 200 by Netzsch The DSC curves were taken whensamples were warmed up with the ramp 10∘Cmin forthe temperature range of 0ndash160∘C To minimize the effectsurface-core extruded samples were cut perpendicularly tothe polymer material flow direction Crystallinity level of
Journal of Nanomaterials 3
the samples was determined using software available for theabovementioned device Netzsch Proteus [23] The programalso enabled testing of the sample melting process in theabovementioned temperature range as well as marking asurface between thermographic curve and a basic line in therange of occurring endothermic peak
The area between the DSC curve and the selected base-line is proportional to the change in enthalpy that is theheat consumed by the sample (endothermic) or released(exothermic) Baselines are mainly used in the calorimetryand mass spectrometry to determine peak heights and areas(enthalpy ion currents and total ion curve) In order to covera multitude of possibilities the Netzsch Proteus programoffers different baseline types For DSC measurements itis usually necessary to correct the measuring values of thebaseline This is obvious when the tested reaction containsnot only a heat of reaction but also a change of specificheat Baseline correction greatly influences the parameters ofinverse reaction kinetics It is also an indication that a neces-sary baseline correction may not be omitted When choosingthe baseline types one must take the physicochemical factsinto consideration The straight baseline joins the start andend values of the chosenmeasuring range with a straight lineexpressed by
119861 (119905) = 119863 (119905119904) +
119863 (119905119891) minus 119863 (119905
119904)
(119905119891minus 119905119904)
(119905 minus 119905119904) (1)
where 119861(119905) is a baseline value 119863(119905) is DSC signal 119905119904is initial
time and 119905119891is final time Relation between heat flow and
enthalpy can be expressed by
Δ119867 =119865
119898 sdot 119870=
int119905119891
119905119904(HF (119905) minus 119861 (119905) 119889119905)
119898 sdot 119870
(2)
where 119867 is entalphy 119865 is a peakrsquos area 119898 is a samplersquos mass119870 is a scale factor (sensitivity of a sensor) and HF is a heatflow
Samples mass was between 7 and 10mg They wereweighted using SARTORIUS weight with 001mg accu-racy internal calibration and closed measurement chamberStructural tests weremade using opticalmicroscope byNikonEclipse E200 For the tests 10ndash18mm thick samples were cutoff from the core applied for DMTA using Thermo ElectronCorporation microtome
Colour tests were made using CIELab method applyingX-rite SP60 calorimeterThe CIELab colour space is the mostfrequently used method to measure colour of not emittinglight objectsThe CIELabmodel is a mathematic transforma-tion of the CIE119883119884119885 space to allow humans to see and distin-guish colours [7]
Tests results were presented in the chromatic coordinates119886 119887 and 119871 Coordinate 119886 determines colour change fromgreen to red while 119887 determines colour change from blue toyellow what was shown in Figure 2
The parameter 119871 (brightness) shows colour change fromblack for 119871 = 0 to white for 119871 = 100 Shine test was madeusing Elcometer 406L Statistical Glossmeter device Reflec-tometric value was taken as a shine measure of the sample
L = 100
L = 0
+a
minusa
+b
minusb
Figure 2 CIELab space
surface which is a relation of light stream reflected fromthe surface to the light stream that falls to this surfaceThis test measured intensity of reflected and dissipated lightfor narrow reflection angle (20∘) Reflected light intensitydepends on the light refraction absorption transparencyand kind of surface The shine measurements results wererepresented in shine units GU (gloss units)
3 Results and Discussion
Figures 3(a)ndash3(c) show thermomechanical curves of poly-ethylene and modified materials that were obtained fromDMTA tests Modulus values and mechanical core losscoefficient are different for investigated materials Providedtests show that modifier diminishes modulus value (Figures3(b) and 3(c)) In the glassy range material is hard and brittlewhich means that thermal energy is insufficient to breakthe barrier for shifting and rotational movement of particlessegmentsThematerial is in the thermodynamical unbalanceThe modulus values decrease for both polyethylene (Fig-ure 3(a)) and modified polyethylene (Figures 3(b) and 3(c))with rising temperature In the glassy transformation rangesome Brown movement in the molecular chain is initiatedThermal energy is becoming comparable with potentialenergy barrier for molecular rotation In the neighborhoodof the glassy transformation temperature the viscoelasticproperties of tested materials are changing fast with the timeand temperature In this range lower values were observedfor lower contents of themodifier (Figure 3(b))Themodulusvalue increases with the higher modifier contents (Fig-ure 3(c)) In the highly elastic entropic strains temperatureinfluence on module 1198641015840 is the same for both tested materialsIn the last range themodule value is very low and thematerialis in the liquid state so it is unable to come back to its previousshape For both materials the same tendency of the modulevalue decrease is observed The mechanical core loss angletangent 119905119892120575 curve looks the same for both materials and
4 Journal of Nanomaterials
000
005
010
015
020
025
030
0 4020 8060 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000
E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(a)
000
005
010
015
020
025
030
0 4020 8060 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(b)
000
005
010
015
020
025
030
035
0 4020 60 80 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000
E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(c)
Figure 3 The dependence of the storage modulus value andmechanical loss tangent versus temperature of tested materials (a)PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier
considered vibration frequencies The only difference relatesto the slight movement of its value corresponding to themaximum temperature for the material with higher contentsof the modifier (Figure 3(c)) Considering the mechanicalcore loss angle tangent 119905119892120575 curve we can notice that materialwith 1 contents of the modifier shows better dampingproperties when compared with the material with its lowercontents or not modified
Figure 4 presents the DSC thermograms for tested mate-rials
For sample with added modifier amount of absorbedenergy was diminishing Also melting enthalpy for modifiedmaterials was changing
The crystallinity degree of the material was decreasingwith the higher contents of the modifier The maximalmelting and crystallizing temperature was the same for bothmaterials while the melting temperature range as well as thecrystallizing temperature range was narrowing
Likely the crystallite level change for modified polyethy-lene was caused by diminishing number of heterogenousnucleation centres With higher amount of modifier and lessnucleation process the crystal phase growth of the polymerbase was reduced Somemodifiers added to semicrystal poly-mer increase base crystalizing temperature and affect dimin-ishing crystallites size while changing participation of thecrystal phase [24 25]
Investigated structure of both materials showed frag-mentation of the crystalline structure (Figure 5) Whenpolyethylene is compared with other semicrystalline plasticsit reveals quite well developed structure with visible shapebig spherulite (Figure 5(a)) Optical microscope observationof the modified materials shows fragmentation of the crystalstructure particularly for higher contents of the modifier(Figure 5(c))
For both pure (Figure 5(a)) and modified (Figures 5(b)and 5(c)) polyethylene the structure is well seen and ordered
Figures 6 7 and 8 show 119871 119886 and 119887 values of testedpolymer materials
The modifier changes the luminance value 119871 It is con-nected with the modifier colour and its contents in thepolymer as well as its discretion and reactivity to polymer Forthe polyethylene with the modifier the 119871 value is decreased(Figure 6) which indicates that the moulders are darker
Increasing amount of the modifier in the polymer effectssome small decrease of its luminance So samples with1 contents of the modifier are a little darker than thosewith 05 contents which indicates smaller influence of themodifier on polymer luminance
Changes of 119886 and 119887 coordinates for tested materials provesignificant influence of the modifier on colour (Figures 7 and8) More modifier contents resulted in higher saturation ofgreen colour in the samples
Results of the shine change of tested materials are pre-sented in Figure 9
The lowest shine values were observed for the highercontents of the modifier in the material
Figure 4 DSC thermograms of (a) PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier Peaklowast means the position of the peakmaximum
6 Journal of Nanomaterials
(a) (b)
(c)
Figure 5 Structures observed on optical microscope with the magnification 350x (a) PE-HD (b) PE-HD05modifier and (c) PE-HD1modifier
75632
58641 55874
3210
10
20
30
40
50
60
70
80
Ligh
tnes
s (cd
m2)
Figure 6The lightness 119871 of the examined polymer materials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1 modifier
4 Conclusion
We observed influence of active SBA-15 silica filler onmechanical properties of high density polyethylene Adding05 and 1 of copper-containing modifier significantlydiminished1198641015840modulus valueThis divergence varies depend-ing on temperature In the same time the loss angle tangentseems to have similar graph for pure HDPE and modifiedmaterial The only difference is in slight shift of maximum
0 1 2 3
minus1095
minus1916
minus7437
minus1
minus2
minus3
minus4
minus5
minus6
minus7
minus8
ldquoardquo c
oord
inat
e
Figure 7 The value of 119886 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
losses in the case of modified sample Material containing 1of modifier has better dumping properties than pure HDPE
DSC research showed that adding of silica modifiersignificantly decreases crystallinity of the polyethylene whilemaximum temperature of melting and crystallization staysunchanged Nevertheless after adding filler the range ofmelting and crystallization temperature was narrowed
The colour of the modified samples changed significantlyAfter adding copper-containing silica modifier samples
Journal of Nanomaterials 7
27742
21636
0
5
10
15
20
25
30
12 3
minus5
minus10
ldquobrdquo c
oord
inat
e
minus3482
Figure 8 The value of 119887 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
2504
1300
897
0
5
10
15
20
25
30
Glo
ss
1 2 3
Figure 9 Gloss of the examined polymer materials 1 PE-HD 2PE-HD05 modifier and 3 PE-HD1 modifier
become green with colour saturation depending on the fillercontents Also the gloss of the material changed as aresult of modification With increasing modifier contents weobserved decreasing HDPE gloss
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
Financial support for this investigation has been providedby the National Centre of Science (Grant no 201103DST505996)
References
[1] J S Beck J C Vartuli G J Kennedy C T Kresge W J Rothand S E Schramm ldquoMolecular or supramolecular templatingdefining the role of surfactant chemistry in the formation ofmicroporous and mesoporous molecular sievesrdquo Chemistry ofMaterials vol 6 no 10 pp 1816ndash1821 1994
[2] J S Beck J C Vartuli W J Roth et al ldquoA new family of meso-porousmolecular sieves prepared with liquid crystal templatesrdquoJournal of the American Chemical Society vol 114 no 27 pp10834ndash10843 1992
[3] L Giraldo and J C Moreno-Pirajan ldquoCalorimetric study ofmesoporous SBA-15modified for controlled valproic acid deliv-eryrdquo Journal of Chemistry vol 2013 Article ID 267464 11 pages2013
[4] D Halamova M Badanicova V Zelenak T Gondova and UVainio ldquoNaproxen drug delivery using periodic mesoporoussilica SBA-15rdquo Applied Surface Science vol 256 no 22 pp6489ndash6494 2010
[5] J Zhang and J Zhu ldquoA novel amperometric biosensor based ongold nanoparticles-mesoporous silica composite for biosensingglucoserdquo Science in China Series B Chemistry vol 52 no 6 pp815ndash820 2009
[6] Y Park T Kang J Lee P Kim H Kim and J Yi ldquoSingle-steppreparation of Ni catalysts supported on mesoporous silicas(SBA-15 and SBA-16) and the effect of pore structure on theselective hydrodechlorination of 112-trichloroethane to VCMrdquoCatalysis Today vol 97 no 2-3 pp 195ndash203 2004
[7] F-S Xiao ldquoOrdered mesoporous materials with improvedstability and catalytic activityrdquo Topics in Catalysis vol 35 no1-2 pp 9ndash24 2005
[8] G Wirnsberger P Yang B J Scott B F Chmelka and G DStucky ldquoMesostructuredmaterials for optical applications fromlow-k dielectrics to sensors and lasersrdquo SpectrochimicaActa PartA Molecular and Biomolecular Spectroscopy vol 57 no 10 pp2049ndash2060 2001
[9] X Wang and H Yang ldquoA dansyl group modified SBA-15INHIBIT logic gate with [Hg2+ and Clminus] or [Hg2+ and Brminus] asinputsrdquo Applied Surface Science vol 277 pp 257ndash262 2013
[10] L Laskowski and M Laskowska ldquoFunctionalization of SBA-15mesoporous silica by Cu-phosphonate units probing of synthe-sis routerdquo Journal of Solid State Chemistry vol 220 pp 221ndash2262014
[11] J P Ruparelia A K Chatterjee S P Duttagupta and SMukherji ldquoStrain specificity in antimicrobial activity of silverand copper nanoparticlesrdquo Acta Biomaterialia vol 4 no 3 pp707ndash716 2008
[12] L Argueta-Figueroa R A Morales-Luckie R J Scougall-Vilchis and O F Olea-Mejıa ldquoSynthesis characterization andantibacterial activity of copper nickel and bimetallic CundashNinanoparticles for potential use in dental materialsrdquo Progress inNatural Science Materials International vol 24 no 4 pp 321ndash328 2014
[13] M Laskowska L Laskowski K Fijałkowski and M KacprzakldquoSynteza i własciwosci fizykochemiczne krzemionki typu SBA-15 aktywowanej jonamimiedzirdquo InzynieriaMateriałowa vol 35no 6 pp 516ndash518 2014
[14] H Blom R Yeh R Wojnarowski and M Ling ldquoDetection ofdegradation of ABS materials via DSCrdquo Thermochimica Actavol 442 no 1-2 pp 64ndash66 A collection of papers from the 32ndConference ofNorthAmericanThermal Analysis Society 2006
[15] A Gnatowski and J Koszkul ldquoInvestigations of the influenceof compatibilizer and filler type on the properties of chosenpolymer blendsrdquo Journal ofMaterials Processing Technology vol162-163 pp 52ndash58 2005
[16] A Gnatowski and J Koszkul ldquoInvestigation on PAPP mixtureproperties by means of DMTA methodrdquo Journal of MaterialsProcessing Technology vol 175 no 1ndash3 pp 212ndash217 2006
8 Journal of Nanomaterials
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
plastics by adding fillers seems to be relatively simple it issufficient to add considered filler into the plastic duringmelt-ing process Nevertheless fillers can modify also mechanicalproperties of plastics which can transfer to their commercialuse constraints In the paper we present the influence ofthe copper-containing SBA-15 silica filler on the mechanicalproperties of the high density polyethylene (HDPE)
The features of modified material depend on structuralfactors of polymer as well as added modifier The struc-tural factors are mainly molecular weight macromolecularchemical structure physical layout of a chain crystallinityand molecular orientation while conditions of use are tem-perature load time pressure strain type and so on [14ndash19] Estimation of possible feature changes of these materi-als with added modifiers plays important role in polymermaterials composition Technical and economical usabilityof polymer materials depends on their required stiffnessand strength to fulfil durability condition Typically obtainedmechanical characteristics when material is statically loadedstretched compressed or twisted are not sufficient to pre-dict its behaviour in extreme condition of usage and longexploitation time Selection of research methods that enableprediction of material viscoelastic features change with thetime based on experimental data is still an open problemAs tested materials are viscoelastic all factors related totheir physicomechanical features deeply depend on time andtemperature So applied research methods must considerthese dependencies One of thesemethods is thermal analysisof mechanical features dynamics (DMTA) It is used tomeasure the relaxation modules versus time with constanttemperature and as a function of load change frequency andtemperature [16 19ndash22] Mechanical characteristics obtainedfor statical load at room temperature are not adequate to esti-mate materialrsquos features in any other conditions of usage [1619ndash22]The way to recognise all properties of tested materialsand estimate their behaviour in predicted usage conditionsis to obtain for them viscoelastic functions that contain allrequired thermal and time dependencies Sinusoidal wayof loading applied for tests is similar to load schemes inpracticeThermal analysis ofmechanical properties dynamics(DMTA) is one of the common schemes to evaluate changesin polymer materials for wide temperature range and loadfrequency variation As an effect of this analysis we getprocess of dynamic Young modules changes and mechanicalcore loss angle tangent modification Being familiar withthese dependencies allows us to find relationship betweenmolecular parameters and mechanical properties of polymermaterials [16 19ndash22] In the paper we presented the followingproperties of created materials mechanical dynamics ther-mal properties shine and structure
2 Materials and Methods
For test we used polyethylene Hostalen GC 7260 manu-factured by Lyondell and Basell with 05 and 1 fillerof mesoporous SBA-15 silica containing propyl-phosphonateunits activated by copper ions in the form of powder Thefiller was prepared according to the procedure described in[10] To obtain composite we mechanically stirred polymer
Oscillator Force
Displacementsensor
Adjustment withstepper motor
Force signal
DisplacementProbe
Displacementdevice
Sample holder
Sample
Control
Sample
Heatingcooling
signal
thermocouple
thermocouple
Figure 1 The scheme of the device for the three-point bending ofsample
withmodifier andmade it more flexible with a help of a screwextruder Then the material was granulated We applied thefollowing parameters of the composite extrusion
(i) Screw rotational speed 250mms(ii) Nozzle temperature 200∘C
The abovementioned procedure was applied for both PE-HD + 05 weight of modifier and PE-HD + 1 weight ofmodifier Samples were obtained on the extruder KRAUSSMAFFEI KM65-160C1 Applied extrusion parameters for allsamples were as follows maximal pressure in the plasticiserpart 60MPa extrusion time 06 s clamps pressure 30MPaclamps time 28 s cooling time 15 s dozing time 66 s formclosing force 650 kN form temperature minus40∘C and extrusiontemperature 195∘C
Dynamic mechanical properties were tested with a helpof DMA 242 device manufactured by Netzsch with three-point free bent grip handle of the beam sample as it wasdepicted in Figure 1 Applied bent frequency was 1 and 10Hzat temperature range of minus150ndash140∘C with heating ramp of2∘Cmin
On the basis of the force value and the sample strainincluding its size value of modulus 1198641015840 the loss module 11986410158401015840and mechanical core loss angle tangent 119905119892120575 were calculatedObtained results were presented in the form of diagrams ofthe abovementioned quantities versus temperature and vibra-tion frequencyThermal properties of the samples were testedusing DSC method while their structure was observed withgoing through light by optical microscope
TheDSC tests were made using scanning microcalorime-ter type 200 by Netzsch The DSC curves were taken whensamples were warmed up with the ramp 10∘Cmin forthe temperature range of 0ndash160∘C To minimize the effectsurface-core extruded samples were cut perpendicularly tothe polymer material flow direction Crystallinity level of
Journal of Nanomaterials 3
the samples was determined using software available for theabovementioned device Netzsch Proteus [23] The programalso enabled testing of the sample melting process in theabovementioned temperature range as well as marking asurface between thermographic curve and a basic line in therange of occurring endothermic peak
The area between the DSC curve and the selected base-line is proportional to the change in enthalpy that is theheat consumed by the sample (endothermic) or released(exothermic) Baselines are mainly used in the calorimetryand mass spectrometry to determine peak heights and areas(enthalpy ion currents and total ion curve) In order to covera multitude of possibilities the Netzsch Proteus programoffers different baseline types For DSC measurements itis usually necessary to correct the measuring values of thebaseline This is obvious when the tested reaction containsnot only a heat of reaction but also a change of specificheat Baseline correction greatly influences the parameters ofinverse reaction kinetics It is also an indication that a neces-sary baseline correction may not be omitted When choosingthe baseline types one must take the physicochemical factsinto consideration The straight baseline joins the start andend values of the chosenmeasuring range with a straight lineexpressed by
119861 (119905) = 119863 (119905119904) +
119863 (119905119891) minus 119863 (119905
119904)
(119905119891minus 119905119904)
(119905 minus 119905119904) (1)
where 119861(119905) is a baseline value 119863(119905) is DSC signal 119905119904is initial
time and 119905119891is final time Relation between heat flow and
enthalpy can be expressed by
Δ119867 =119865
119898 sdot 119870=
int119905119891
119905119904(HF (119905) minus 119861 (119905) 119889119905)
119898 sdot 119870
(2)
where 119867 is entalphy 119865 is a peakrsquos area 119898 is a samplersquos mass119870 is a scale factor (sensitivity of a sensor) and HF is a heatflow
Samples mass was between 7 and 10mg They wereweighted using SARTORIUS weight with 001mg accu-racy internal calibration and closed measurement chamberStructural tests weremade using opticalmicroscope byNikonEclipse E200 For the tests 10ndash18mm thick samples were cutoff from the core applied for DMTA using Thermo ElectronCorporation microtome
Colour tests were made using CIELab method applyingX-rite SP60 calorimeterThe CIELab colour space is the mostfrequently used method to measure colour of not emittinglight objectsThe CIELabmodel is a mathematic transforma-tion of the CIE119883119884119885 space to allow humans to see and distin-guish colours [7]
Tests results were presented in the chromatic coordinates119886 119887 and 119871 Coordinate 119886 determines colour change fromgreen to red while 119887 determines colour change from blue toyellow what was shown in Figure 2
The parameter 119871 (brightness) shows colour change fromblack for 119871 = 0 to white for 119871 = 100 Shine test was madeusing Elcometer 406L Statistical Glossmeter device Reflec-tometric value was taken as a shine measure of the sample
L = 100
L = 0
+a
minusa
+b
minusb
Figure 2 CIELab space
surface which is a relation of light stream reflected fromthe surface to the light stream that falls to this surfaceThis test measured intensity of reflected and dissipated lightfor narrow reflection angle (20∘) Reflected light intensitydepends on the light refraction absorption transparencyand kind of surface The shine measurements results wererepresented in shine units GU (gloss units)
3 Results and Discussion
Figures 3(a)ndash3(c) show thermomechanical curves of poly-ethylene and modified materials that were obtained fromDMTA tests Modulus values and mechanical core losscoefficient are different for investigated materials Providedtests show that modifier diminishes modulus value (Figures3(b) and 3(c)) In the glassy range material is hard and brittlewhich means that thermal energy is insufficient to breakthe barrier for shifting and rotational movement of particlessegmentsThematerial is in the thermodynamical unbalanceThe modulus values decrease for both polyethylene (Fig-ure 3(a)) and modified polyethylene (Figures 3(b) and 3(c))with rising temperature In the glassy transformation rangesome Brown movement in the molecular chain is initiatedThermal energy is becoming comparable with potentialenergy barrier for molecular rotation In the neighborhoodof the glassy transformation temperature the viscoelasticproperties of tested materials are changing fast with the timeand temperature In this range lower values were observedfor lower contents of themodifier (Figure 3(b))Themodulusvalue increases with the higher modifier contents (Fig-ure 3(c)) In the highly elastic entropic strains temperatureinfluence on module 1198641015840 is the same for both tested materialsIn the last range themodule value is very low and thematerialis in the liquid state so it is unable to come back to its previousshape For both materials the same tendency of the modulevalue decrease is observed The mechanical core loss angletangent 119905119892120575 curve looks the same for both materials and
4 Journal of Nanomaterials
000
005
010
015
020
025
030
0 4020 8060 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000
E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(a)
000
005
010
015
020
025
030
0 4020 8060 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(b)
000
005
010
015
020
025
030
035
0 4020 60 80 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000
E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(c)
Figure 3 The dependence of the storage modulus value andmechanical loss tangent versus temperature of tested materials (a)PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier
considered vibration frequencies The only difference relatesto the slight movement of its value corresponding to themaximum temperature for the material with higher contentsof the modifier (Figure 3(c)) Considering the mechanicalcore loss angle tangent 119905119892120575 curve we can notice that materialwith 1 contents of the modifier shows better dampingproperties when compared with the material with its lowercontents or not modified
Figure 4 presents the DSC thermograms for tested mate-rials
For sample with added modifier amount of absorbedenergy was diminishing Also melting enthalpy for modifiedmaterials was changing
The crystallinity degree of the material was decreasingwith the higher contents of the modifier The maximalmelting and crystallizing temperature was the same for bothmaterials while the melting temperature range as well as thecrystallizing temperature range was narrowing
Likely the crystallite level change for modified polyethy-lene was caused by diminishing number of heterogenousnucleation centres With higher amount of modifier and lessnucleation process the crystal phase growth of the polymerbase was reduced Somemodifiers added to semicrystal poly-mer increase base crystalizing temperature and affect dimin-ishing crystallites size while changing participation of thecrystal phase [24 25]
Investigated structure of both materials showed frag-mentation of the crystalline structure (Figure 5) Whenpolyethylene is compared with other semicrystalline plasticsit reveals quite well developed structure with visible shapebig spherulite (Figure 5(a)) Optical microscope observationof the modified materials shows fragmentation of the crystalstructure particularly for higher contents of the modifier(Figure 5(c))
For both pure (Figure 5(a)) and modified (Figures 5(b)and 5(c)) polyethylene the structure is well seen and ordered
Figures 6 7 and 8 show 119871 119886 and 119887 values of testedpolymer materials
The modifier changes the luminance value 119871 It is con-nected with the modifier colour and its contents in thepolymer as well as its discretion and reactivity to polymer Forthe polyethylene with the modifier the 119871 value is decreased(Figure 6) which indicates that the moulders are darker
Increasing amount of the modifier in the polymer effectssome small decrease of its luminance So samples with1 contents of the modifier are a little darker than thosewith 05 contents which indicates smaller influence of themodifier on polymer luminance
Changes of 119886 and 119887 coordinates for tested materials provesignificant influence of the modifier on colour (Figures 7 and8) More modifier contents resulted in higher saturation ofgreen colour in the samples
Results of the shine change of tested materials are pre-sented in Figure 9
The lowest shine values were observed for the highercontents of the modifier in the material
Figure 4 DSC thermograms of (a) PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier Peaklowast means the position of the peakmaximum
6 Journal of Nanomaterials
(a) (b)
(c)
Figure 5 Structures observed on optical microscope with the magnification 350x (a) PE-HD (b) PE-HD05modifier and (c) PE-HD1modifier
75632
58641 55874
3210
10
20
30
40
50
60
70
80
Ligh
tnes
s (cd
m2)
Figure 6The lightness 119871 of the examined polymer materials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1 modifier
4 Conclusion
We observed influence of active SBA-15 silica filler onmechanical properties of high density polyethylene Adding05 and 1 of copper-containing modifier significantlydiminished1198641015840modulus valueThis divergence varies depend-ing on temperature In the same time the loss angle tangentseems to have similar graph for pure HDPE and modifiedmaterial The only difference is in slight shift of maximum
0 1 2 3
minus1095
minus1916
minus7437
minus1
minus2
minus3
minus4
minus5
minus6
minus7
minus8
ldquoardquo c
oord
inat
e
Figure 7 The value of 119886 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
losses in the case of modified sample Material containing 1of modifier has better dumping properties than pure HDPE
DSC research showed that adding of silica modifiersignificantly decreases crystallinity of the polyethylene whilemaximum temperature of melting and crystallization staysunchanged Nevertheless after adding filler the range ofmelting and crystallization temperature was narrowed
The colour of the modified samples changed significantlyAfter adding copper-containing silica modifier samples
Journal of Nanomaterials 7
27742
21636
0
5
10
15
20
25
30
12 3
minus5
minus10
ldquobrdquo c
oord
inat
e
minus3482
Figure 8 The value of 119887 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
2504
1300
897
0
5
10
15
20
25
30
Glo
ss
1 2 3
Figure 9 Gloss of the examined polymer materials 1 PE-HD 2PE-HD05 modifier and 3 PE-HD1 modifier
become green with colour saturation depending on the fillercontents Also the gloss of the material changed as aresult of modification With increasing modifier contents weobserved decreasing HDPE gloss
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
Financial support for this investigation has been providedby the National Centre of Science (Grant no 201103DST505996)
References
[1] J S Beck J C Vartuli G J Kennedy C T Kresge W J Rothand S E Schramm ldquoMolecular or supramolecular templatingdefining the role of surfactant chemistry in the formation ofmicroporous and mesoporous molecular sievesrdquo Chemistry ofMaterials vol 6 no 10 pp 1816ndash1821 1994
[2] J S Beck J C Vartuli W J Roth et al ldquoA new family of meso-porousmolecular sieves prepared with liquid crystal templatesrdquoJournal of the American Chemical Society vol 114 no 27 pp10834ndash10843 1992
[3] L Giraldo and J C Moreno-Pirajan ldquoCalorimetric study ofmesoporous SBA-15modified for controlled valproic acid deliv-eryrdquo Journal of Chemistry vol 2013 Article ID 267464 11 pages2013
[4] D Halamova M Badanicova V Zelenak T Gondova and UVainio ldquoNaproxen drug delivery using periodic mesoporoussilica SBA-15rdquo Applied Surface Science vol 256 no 22 pp6489ndash6494 2010
[5] J Zhang and J Zhu ldquoA novel amperometric biosensor based ongold nanoparticles-mesoporous silica composite for biosensingglucoserdquo Science in China Series B Chemistry vol 52 no 6 pp815ndash820 2009
[6] Y Park T Kang J Lee P Kim H Kim and J Yi ldquoSingle-steppreparation of Ni catalysts supported on mesoporous silicas(SBA-15 and SBA-16) and the effect of pore structure on theselective hydrodechlorination of 112-trichloroethane to VCMrdquoCatalysis Today vol 97 no 2-3 pp 195ndash203 2004
[7] F-S Xiao ldquoOrdered mesoporous materials with improvedstability and catalytic activityrdquo Topics in Catalysis vol 35 no1-2 pp 9ndash24 2005
[8] G Wirnsberger P Yang B J Scott B F Chmelka and G DStucky ldquoMesostructuredmaterials for optical applications fromlow-k dielectrics to sensors and lasersrdquo SpectrochimicaActa PartA Molecular and Biomolecular Spectroscopy vol 57 no 10 pp2049ndash2060 2001
[9] X Wang and H Yang ldquoA dansyl group modified SBA-15INHIBIT logic gate with [Hg2+ and Clminus] or [Hg2+ and Brminus] asinputsrdquo Applied Surface Science vol 277 pp 257ndash262 2013
[10] L Laskowski and M Laskowska ldquoFunctionalization of SBA-15mesoporous silica by Cu-phosphonate units probing of synthe-sis routerdquo Journal of Solid State Chemistry vol 220 pp 221ndash2262014
[11] J P Ruparelia A K Chatterjee S P Duttagupta and SMukherji ldquoStrain specificity in antimicrobial activity of silverand copper nanoparticlesrdquo Acta Biomaterialia vol 4 no 3 pp707ndash716 2008
[12] L Argueta-Figueroa R A Morales-Luckie R J Scougall-Vilchis and O F Olea-Mejıa ldquoSynthesis characterization andantibacterial activity of copper nickel and bimetallic CundashNinanoparticles for potential use in dental materialsrdquo Progress inNatural Science Materials International vol 24 no 4 pp 321ndash328 2014
[13] M Laskowska L Laskowski K Fijałkowski and M KacprzakldquoSynteza i własciwosci fizykochemiczne krzemionki typu SBA-15 aktywowanej jonamimiedzirdquo InzynieriaMateriałowa vol 35no 6 pp 516ndash518 2014
[14] H Blom R Yeh R Wojnarowski and M Ling ldquoDetection ofdegradation of ABS materials via DSCrdquo Thermochimica Actavol 442 no 1-2 pp 64ndash66 A collection of papers from the 32ndConference ofNorthAmericanThermal Analysis Society 2006
[15] A Gnatowski and J Koszkul ldquoInvestigations of the influenceof compatibilizer and filler type on the properties of chosenpolymer blendsrdquo Journal ofMaterials Processing Technology vol162-163 pp 52ndash58 2005
[16] A Gnatowski and J Koszkul ldquoInvestigation on PAPP mixtureproperties by means of DMTA methodrdquo Journal of MaterialsProcessing Technology vol 175 no 1ndash3 pp 212ndash217 2006
8 Journal of Nanomaterials
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
the samples was determined using software available for theabovementioned device Netzsch Proteus [23] The programalso enabled testing of the sample melting process in theabovementioned temperature range as well as marking asurface between thermographic curve and a basic line in therange of occurring endothermic peak
The area between the DSC curve and the selected base-line is proportional to the change in enthalpy that is theheat consumed by the sample (endothermic) or released(exothermic) Baselines are mainly used in the calorimetryand mass spectrometry to determine peak heights and areas(enthalpy ion currents and total ion curve) In order to covera multitude of possibilities the Netzsch Proteus programoffers different baseline types For DSC measurements itis usually necessary to correct the measuring values of thebaseline This is obvious when the tested reaction containsnot only a heat of reaction but also a change of specificheat Baseline correction greatly influences the parameters ofinverse reaction kinetics It is also an indication that a neces-sary baseline correction may not be omitted When choosingthe baseline types one must take the physicochemical factsinto consideration The straight baseline joins the start andend values of the chosenmeasuring range with a straight lineexpressed by
119861 (119905) = 119863 (119905119904) +
119863 (119905119891) minus 119863 (119905
119904)
(119905119891minus 119905119904)
(119905 minus 119905119904) (1)
where 119861(119905) is a baseline value 119863(119905) is DSC signal 119905119904is initial
time and 119905119891is final time Relation between heat flow and
enthalpy can be expressed by
Δ119867 =119865
119898 sdot 119870=
int119905119891
119905119904(HF (119905) minus 119861 (119905) 119889119905)
119898 sdot 119870
(2)
where 119867 is entalphy 119865 is a peakrsquos area 119898 is a samplersquos mass119870 is a scale factor (sensitivity of a sensor) and HF is a heatflow
Samples mass was between 7 and 10mg They wereweighted using SARTORIUS weight with 001mg accu-racy internal calibration and closed measurement chamberStructural tests weremade using opticalmicroscope byNikonEclipse E200 For the tests 10ndash18mm thick samples were cutoff from the core applied for DMTA using Thermo ElectronCorporation microtome
Colour tests were made using CIELab method applyingX-rite SP60 calorimeterThe CIELab colour space is the mostfrequently used method to measure colour of not emittinglight objectsThe CIELabmodel is a mathematic transforma-tion of the CIE119883119884119885 space to allow humans to see and distin-guish colours [7]
Tests results were presented in the chromatic coordinates119886 119887 and 119871 Coordinate 119886 determines colour change fromgreen to red while 119887 determines colour change from blue toyellow what was shown in Figure 2
The parameter 119871 (brightness) shows colour change fromblack for 119871 = 0 to white for 119871 = 100 Shine test was madeusing Elcometer 406L Statistical Glossmeter device Reflec-tometric value was taken as a shine measure of the sample
L = 100
L = 0
+a
minusa
+b
minusb
Figure 2 CIELab space
surface which is a relation of light stream reflected fromthe surface to the light stream that falls to this surfaceThis test measured intensity of reflected and dissipated lightfor narrow reflection angle (20∘) Reflected light intensitydepends on the light refraction absorption transparencyand kind of surface The shine measurements results wererepresented in shine units GU (gloss units)
3 Results and Discussion
Figures 3(a)ndash3(c) show thermomechanical curves of poly-ethylene and modified materials that were obtained fromDMTA tests Modulus values and mechanical core losscoefficient are different for investigated materials Providedtests show that modifier diminishes modulus value (Figures3(b) and 3(c)) In the glassy range material is hard and brittlewhich means that thermal energy is insufficient to breakthe barrier for shifting and rotational movement of particlessegmentsThematerial is in the thermodynamical unbalanceThe modulus values decrease for both polyethylene (Fig-ure 3(a)) and modified polyethylene (Figures 3(b) and 3(c))with rising temperature In the glassy transformation rangesome Brown movement in the molecular chain is initiatedThermal energy is becoming comparable with potentialenergy barrier for molecular rotation In the neighborhoodof the glassy transformation temperature the viscoelasticproperties of tested materials are changing fast with the timeand temperature In this range lower values were observedfor lower contents of themodifier (Figure 3(b))Themodulusvalue increases with the higher modifier contents (Fig-ure 3(c)) In the highly elastic entropic strains temperatureinfluence on module 1198641015840 is the same for both tested materialsIn the last range themodule value is very low and thematerialis in the liquid state so it is unable to come back to its previousshape For both materials the same tendency of the modulevalue decrease is observed The mechanical core loss angletangent 119905119892120575 curve looks the same for both materials and
4 Journal of Nanomaterials
000
005
010
015
020
025
030
0 4020 8060 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000
E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(a)
000
005
010
015
020
025
030
0 4020 8060 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(b)
000
005
010
015
020
025
030
035
0 4020 60 80 100
120
140
minus20
minus80
minus60
minus40
minus120
minus100
minus140
Temperature (∘C)E998400 (1Hz)
E998400 (10Hz)
0
1000
2000
3000
4000
5000
E998400
(MPa
)
tan 120575
tan 120575 (10 Hz)tan 120575 (1Hz)
(c)
Figure 3 The dependence of the storage modulus value andmechanical loss tangent versus temperature of tested materials (a)PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier
considered vibration frequencies The only difference relatesto the slight movement of its value corresponding to themaximum temperature for the material with higher contentsof the modifier (Figure 3(c)) Considering the mechanicalcore loss angle tangent 119905119892120575 curve we can notice that materialwith 1 contents of the modifier shows better dampingproperties when compared with the material with its lowercontents or not modified
Figure 4 presents the DSC thermograms for tested mate-rials
For sample with added modifier amount of absorbedenergy was diminishing Also melting enthalpy for modifiedmaterials was changing
The crystallinity degree of the material was decreasingwith the higher contents of the modifier The maximalmelting and crystallizing temperature was the same for bothmaterials while the melting temperature range as well as thecrystallizing temperature range was narrowing
Likely the crystallite level change for modified polyethy-lene was caused by diminishing number of heterogenousnucleation centres With higher amount of modifier and lessnucleation process the crystal phase growth of the polymerbase was reduced Somemodifiers added to semicrystal poly-mer increase base crystalizing temperature and affect dimin-ishing crystallites size while changing participation of thecrystal phase [24 25]
Investigated structure of both materials showed frag-mentation of the crystalline structure (Figure 5) Whenpolyethylene is compared with other semicrystalline plasticsit reveals quite well developed structure with visible shapebig spherulite (Figure 5(a)) Optical microscope observationof the modified materials shows fragmentation of the crystalstructure particularly for higher contents of the modifier(Figure 5(c))
For both pure (Figure 5(a)) and modified (Figures 5(b)and 5(c)) polyethylene the structure is well seen and ordered
Figures 6 7 and 8 show 119871 119886 and 119887 values of testedpolymer materials
The modifier changes the luminance value 119871 It is con-nected with the modifier colour and its contents in thepolymer as well as its discretion and reactivity to polymer Forthe polyethylene with the modifier the 119871 value is decreased(Figure 6) which indicates that the moulders are darker
Increasing amount of the modifier in the polymer effectssome small decrease of its luminance So samples with1 contents of the modifier are a little darker than thosewith 05 contents which indicates smaller influence of themodifier on polymer luminance
Changes of 119886 and 119887 coordinates for tested materials provesignificant influence of the modifier on colour (Figures 7 and8) More modifier contents resulted in higher saturation ofgreen colour in the samples
Results of the shine change of tested materials are pre-sented in Figure 9
The lowest shine values were observed for the highercontents of the modifier in the material
Figure 4 DSC thermograms of (a) PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier Peaklowast means the position of the peakmaximum
6 Journal of Nanomaterials
(a) (b)
(c)
Figure 5 Structures observed on optical microscope with the magnification 350x (a) PE-HD (b) PE-HD05modifier and (c) PE-HD1modifier
75632
58641 55874
3210
10
20
30
40
50
60
70
80
Ligh
tnes
s (cd
m2)
Figure 6The lightness 119871 of the examined polymer materials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1 modifier
4 Conclusion
We observed influence of active SBA-15 silica filler onmechanical properties of high density polyethylene Adding05 and 1 of copper-containing modifier significantlydiminished1198641015840modulus valueThis divergence varies depend-ing on temperature In the same time the loss angle tangentseems to have similar graph for pure HDPE and modifiedmaterial The only difference is in slight shift of maximum
0 1 2 3
minus1095
minus1916
minus7437
minus1
minus2
minus3
minus4
minus5
minus6
minus7
minus8
ldquoardquo c
oord
inat
e
Figure 7 The value of 119886 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
losses in the case of modified sample Material containing 1of modifier has better dumping properties than pure HDPE
DSC research showed that adding of silica modifiersignificantly decreases crystallinity of the polyethylene whilemaximum temperature of melting and crystallization staysunchanged Nevertheless after adding filler the range ofmelting and crystallization temperature was narrowed
The colour of the modified samples changed significantlyAfter adding copper-containing silica modifier samples
Journal of Nanomaterials 7
27742
21636
0
5
10
15
20
25
30
12 3
minus5
minus10
ldquobrdquo c
oord
inat
e
minus3482
Figure 8 The value of 119887 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
2504
1300
897
0
5
10
15
20
25
30
Glo
ss
1 2 3
Figure 9 Gloss of the examined polymer materials 1 PE-HD 2PE-HD05 modifier and 3 PE-HD1 modifier
become green with colour saturation depending on the fillercontents Also the gloss of the material changed as aresult of modification With increasing modifier contents weobserved decreasing HDPE gloss
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
Financial support for this investigation has been providedby the National Centre of Science (Grant no 201103DST505996)
References
[1] J S Beck J C Vartuli G J Kennedy C T Kresge W J Rothand S E Schramm ldquoMolecular or supramolecular templatingdefining the role of surfactant chemistry in the formation ofmicroporous and mesoporous molecular sievesrdquo Chemistry ofMaterials vol 6 no 10 pp 1816ndash1821 1994
[2] J S Beck J C Vartuli W J Roth et al ldquoA new family of meso-porousmolecular sieves prepared with liquid crystal templatesrdquoJournal of the American Chemical Society vol 114 no 27 pp10834ndash10843 1992
[3] L Giraldo and J C Moreno-Pirajan ldquoCalorimetric study ofmesoporous SBA-15modified for controlled valproic acid deliv-eryrdquo Journal of Chemistry vol 2013 Article ID 267464 11 pages2013
[4] D Halamova M Badanicova V Zelenak T Gondova and UVainio ldquoNaproxen drug delivery using periodic mesoporoussilica SBA-15rdquo Applied Surface Science vol 256 no 22 pp6489ndash6494 2010
[5] J Zhang and J Zhu ldquoA novel amperometric biosensor based ongold nanoparticles-mesoporous silica composite for biosensingglucoserdquo Science in China Series B Chemistry vol 52 no 6 pp815ndash820 2009
[6] Y Park T Kang J Lee P Kim H Kim and J Yi ldquoSingle-steppreparation of Ni catalysts supported on mesoporous silicas(SBA-15 and SBA-16) and the effect of pore structure on theselective hydrodechlorination of 112-trichloroethane to VCMrdquoCatalysis Today vol 97 no 2-3 pp 195ndash203 2004
[7] F-S Xiao ldquoOrdered mesoporous materials with improvedstability and catalytic activityrdquo Topics in Catalysis vol 35 no1-2 pp 9ndash24 2005
[8] G Wirnsberger P Yang B J Scott B F Chmelka and G DStucky ldquoMesostructuredmaterials for optical applications fromlow-k dielectrics to sensors and lasersrdquo SpectrochimicaActa PartA Molecular and Biomolecular Spectroscopy vol 57 no 10 pp2049ndash2060 2001
[9] X Wang and H Yang ldquoA dansyl group modified SBA-15INHIBIT logic gate with [Hg2+ and Clminus] or [Hg2+ and Brminus] asinputsrdquo Applied Surface Science vol 277 pp 257ndash262 2013
[10] L Laskowski and M Laskowska ldquoFunctionalization of SBA-15mesoporous silica by Cu-phosphonate units probing of synthe-sis routerdquo Journal of Solid State Chemistry vol 220 pp 221ndash2262014
[11] J P Ruparelia A K Chatterjee S P Duttagupta and SMukherji ldquoStrain specificity in antimicrobial activity of silverand copper nanoparticlesrdquo Acta Biomaterialia vol 4 no 3 pp707ndash716 2008
[12] L Argueta-Figueroa R A Morales-Luckie R J Scougall-Vilchis and O F Olea-Mejıa ldquoSynthesis characterization andantibacterial activity of copper nickel and bimetallic CundashNinanoparticles for potential use in dental materialsrdquo Progress inNatural Science Materials International vol 24 no 4 pp 321ndash328 2014
[13] M Laskowska L Laskowski K Fijałkowski and M KacprzakldquoSynteza i własciwosci fizykochemiczne krzemionki typu SBA-15 aktywowanej jonamimiedzirdquo InzynieriaMateriałowa vol 35no 6 pp 516ndash518 2014
[14] H Blom R Yeh R Wojnarowski and M Ling ldquoDetection ofdegradation of ABS materials via DSCrdquo Thermochimica Actavol 442 no 1-2 pp 64ndash66 A collection of papers from the 32ndConference ofNorthAmericanThermal Analysis Society 2006
[15] A Gnatowski and J Koszkul ldquoInvestigations of the influenceof compatibilizer and filler type on the properties of chosenpolymer blendsrdquo Journal ofMaterials Processing Technology vol162-163 pp 52ndash58 2005
[16] A Gnatowski and J Koszkul ldquoInvestigation on PAPP mixtureproperties by means of DMTA methodrdquo Journal of MaterialsProcessing Technology vol 175 no 1ndash3 pp 212ndash217 2006
8 Journal of Nanomaterials
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
Figure 3 The dependence of the storage modulus value andmechanical loss tangent versus temperature of tested materials (a)PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier
considered vibration frequencies The only difference relatesto the slight movement of its value corresponding to themaximum temperature for the material with higher contentsof the modifier (Figure 3(c)) Considering the mechanicalcore loss angle tangent 119905119892120575 curve we can notice that materialwith 1 contents of the modifier shows better dampingproperties when compared with the material with its lowercontents or not modified
Figure 4 presents the DSC thermograms for tested mate-rials
For sample with added modifier amount of absorbedenergy was diminishing Also melting enthalpy for modifiedmaterials was changing
The crystallinity degree of the material was decreasingwith the higher contents of the modifier The maximalmelting and crystallizing temperature was the same for bothmaterials while the melting temperature range as well as thecrystallizing temperature range was narrowing
Likely the crystallite level change for modified polyethy-lene was caused by diminishing number of heterogenousnucleation centres With higher amount of modifier and lessnucleation process the crystal phase growth of the polymerbase was reduced Somemodifiers added to semicrystal poly-mer increase base crystalizing temperature and affect dimin-ishing crystallites size while changing participation of thecrystal phase [24 25]
Investigated structure of both materials showed frag-mentation of the crystalline structure (Figure 5) Whenpolyethylene is compared with other semicrystalline plasticsit reveals quite well developed structure with visible shapebig spherulite (Figure 5(a)) Optical microscope observationof the modified materials shows fragmentation of the crystalstructure particularly for higher contents of the modifier(Figure 5(c))
For both pure (Figure 5(a)) and modified (Figures 5(b)and 5(c)) polyethylene the structure is well seen and ordered
Figures 6 7 and 8 show 119871 119886 and 119887 values of testedpolymer materials
The modifier changes the luminance value 119871 It is con-nected with the modifier colour and its contents in thepolymer as well as its discretion and reactivity to polymer Forthe polyethylene with the modifier the 119871 value is decreased(Figure 6) which indicates that the moulders are darker
Increasing amount of the modifier in the polymer effectssome small decrease of its luminance So samples with1 contents of the modifier are a little darker than thosewith 05 contents which indicates smaller influence of themodifier on polymer luminance
Changes of 119886 and 119887 coordinates for tested materials provesignificant influence of the modifier on colour (Figures 7 and8) More modifier contents resulted in higher saturation ofgreen colour in the samples
Results of the shine change of tested materials are pre-sented in Figure 9
The lowest shine values were observed for the highercontents of the modifier in the material
Figure 4 DSC thermograms of (a) PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier Peaklowast means the position of the peakmaximum
6 Journal of Nanomaterials
(a) (b)
(c)
Figure 5 Structures observed on optical microscope with the magnification 350x (a) PE-HD (b) PE-HD05modifier and (c) PE-HD1modifier
75632
58641 55874
3210
10
20
30
40
50
60
70
80
Ligh
tnes
s (cd
m2)
Figure 6The lightness 119871 of the examined polymer materials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1 modifier
4 Conclusion
We observed influence of active SBA-15 silica filler onmechanical properties of high density polyethylene Adding05 and 1 of copper-containing modifier significantlydiminished1198641015840modulus valueThis divergence varies depend-ing on temperature In the same time the loss angle tangentseems to have similar graph for pure HDPE and modifiedmaterial The only difference is in slight shift of maximum
0 1 2 3
minus1095
minus1916
minus7437
minus1
minus2
minus3
minus4
minus5
minus6
minus7
minus8
ldquoardquo c
oord
inat
e
Figure 7 The value of 119886 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
losses in the case of modified sample Material containing 1of modifier has better dumping properties than pure HDPE
DSC research showed that adding of silica modifiersignificantly decreases crystallinity of the polyethylene whilemaximum temperature of melting and crystallization staysunchanged Nevertheless after adding filler the range ofmelting and crystallization temperature was narrowed
The colour of the modified samples changed significantlyAfter adding copper-containing silica modifier samples
Journal of Nanomaterials 7
27742
21636
0
5
10
15
20
25
30
12 3
minus5
minus10
ldquobrdquo c
oord
inat
e
minus3482
Figure 8 The value of 119887 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
2504
1300
897
0
5
10
15
20
25
30
Glo
ss
1 2 3
Figure 9 Gloss of the examined polymer materials 1 PE-HD 2PE-HD05 modifier and 3 PE-HD1 modifier
become green with colour saturation depending on the fillercontents Also the gloss of the material changed as aresult of modification With increasing modifier contents weobserved decreasing HDPE gloss
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
Financial support for this investigation has been providedby the National Centre of Science (Grant no 201103DST505996)
References
[1] J S Beck J C Vartuli G J Kennedy C T Kresge W J Rothand S E Schramm ldquoMolecular or supramolecular templatingdefining the role of surfactant chemistry in the formation ofmicroporous and mesoporous molecular sievesrdquo Chemistry ofMaterials vol 6 no 10 pp 1816ndash1821 1994
[2] J S Beck J C Vartuli W J Roth et al ldquoA new family of meso-porousmolecular sieves prepared with liquid crystal templatesrdquoJournal of the American Chemical Society vol 114 no 27 pp10834ndash10843 1992
[3] L Giraldo and J C Moreno-Pirajan ldquoCalorimetric study ofmesoporous SBA-15modified for controlled valproic acid deliv-eryrdquo Journal of Chemistry vol 2013 Article ID 267464 11 pages2013
[4] D Halamova M Badanicova V Zelenak T Gondova and UVainio ldquoNaproxen drug delivery using periodic mesoporoussilica SBA-15rdquo Applied Surface Science vol 256 no 22 pp6489ndash6494 2010
[5] J Zhang and J Zhu ldquoA novel amperometric biosensor based ongold nanoparticles-mesoporous silica composite for biosensingglucoserdquo Science in China Series B Chemistry vol 52 no 6 pp815ndash820 2009
[6] Y Park T Kang J Lee P Kim H Kim and J Yi ldquoSingle-steppreparation of Ni catalysts supported on mesoporous silicas(SBA-15 and SBA-16) and the effect of pore structure on theselective hydrodechlorination of 112-trichloroethane to VCMrdquoCatalysis Today vol 97 no 2-3 pp 195ndash203 2004
[7] F-S Xiao ldquoOrdered mesoporous materials with improvedstability and catalytic activityrdquo Topics in Catalysis vol 35 no1-2 pp 9ndash24 2005
[8] G Wirnsberger P Yang B J Scott B F Chmelka and G DStucky ldquoMesostructuredmaterials for optical applications fromlow-k dielectrics to sensors and lasersrdquo SpectrochimicaActa PartA Molecular and Biomolecular Spectroscopy vol 57 no 10 pp2049ndash2060 2001
[9] X Wang and H Yang ldquoA dansyl group modified SBA-15INHIBIT logic gate with [Hg2+ and Clminus] or [Hg2+ and Brminus] asinputsrdquo Applied Surface Science vol 277 pp 257ndash262 2013
[10] L Laskowski and M Laskowska ldquoFunctionalization of SBA-15mesoporous silica by Cu-phosphonate units probing of synthe-sis routerdquo Journal of Solid State Chemistry vol 220 pp 221ndash2262014
[11] J P Ruparelia A K Chatterjee S P Duttagupta and SMukherji ldquoStrain specificity in antimicrobial activity of silverand copper nanoparticlesrdquo Acta Biomaterialia vol 4 no 3 pp707ndash716 2008
[12] L Argueta-Figueroa R A Morales-Luckie R J Scougall-Vilchis and O F Olea-Mejıa ldquoSynthesis characterization andantibacterial activity of copper nickel and bimetallic CundashNinanoparticles for potential use in dental materialsrdquo Progress inNatural Science Materials International vol 24 no 4 pp 321ndash328 2014
[13] M Laskowska L Laskowski K Fijałkowski and M KacprzakldquoSynteza i własciwosci fizykochemiczne krzemionki typu SBA-15 aktywowanej jonamimiedzirdquo InzynieriaMateriałowa vol 35no 6 pp 516ndash518 2014
[14] H Blom R Yeh R Wojnarowski and M Ling ldquoDetection ofdegradation of ABS materials via DSCrdquo Thermochimica Actavol 442 no 1-2 pp 64ndash66 A collection of papers from the 32ndConference ofNorthAmericanThermal Analysis Society 2006
[15] A Gnatowski and J Koszkul ldquoInvestigations of the influenceof compatibilizer and filler type on the properties of chosenpolymer blendsrdquo Journal ofMaterials Processing Technology vol162-163 pp 52ndash58 2005
[16] A Gnatowski and J Koszkul ldquoInvestigation on PAPP mixtureproperties by means of DMTA methodrdquo Journal of MaterialsProcessing Technology vol 175 no 1ndash3 pp 212ndash217 2006
8 Journal of Nanomaterials
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
Figure 4 DSC thermograms of (a) PE-HD (b) PE-HD05 modifier and (c) PE-HD1 modifier Peaklowast means the position of the peakmaximum
6 Journal of Nanomaterials
(a) (b)
(c)
Figure 5 Structures observed on optical microscope with the magnification 350x (a) PE-HD (b) PE-HD05modifier and (c) PE-HD1modifier
75632
58641 55874
3210
10
20
30
40
50
60
70
80
Ligh
tnes
s (cd
m2)
Figure 6The lightness 119871 of the examined polymer materials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1 modifier
4 Conclusion
We observed influence of active SBA-15 silica filler onmechanical properties of high density polyethylene Adding05 and 1 of copper-containing modifier significantlydiminished1198641015840modulus valueThis divergence varies depend-ing on temperature In the same time the loss angle tangentseems to have similar graph for pure HDPE and modifiedmaterial The only difference is in slight shift of maximum
0 1 2 3
minus1095
minus1916
minus7437
minus1
minus2
minus3
minus4
minus5
minus6
minus7
minus8
ldquoardquo c
oord
inat
e
Figure 7 The value of 119886 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
losses in the case of modified sample Material containing 1of modifier has better dumping properties than pure HDPE
DSC research showed that adding of silica modifiersignificantly decreases crystallinity of the polyethylene whilemaximum temperature of melting and crystallization staysunchanged Nevertheless after adding filler the range ofmelting and crystallization temperature was narrowed
The colour of the modified samples changed significantlyAfter adding copper-containing silica modifier samples
Journal of Nanomaterials 7
27742
21636
0
5
10
15
20
25
30
12 3
minus5
minus10
ldquobrdquo c
oord
inat
e
minus3482
Figure 8 The value of 119887 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
2504
1300
897
0
5
10
15
20
25
30
Glo
ss
1 2 3
Figure 9 Gloss of the examined polymer materials 1 PE-HD 2PE-HD05 modifier and 3 PE-HD1 modifier
become green with colour saturation depending on the fillercontents Also the gloss of the material changed as aresult of modification With increasing modifier contents weobserved decreasing HDPE gloss
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
Financial support for this investigation has been providedby the National Centre of Science (Grant no 201103DST505996)
References
[1] J S Beck J C Vartuli G J Kennedy C T Kresge W J Rothand S E Schramm ldquoMolecular or supramolecular templatingdefining the role of surfactant chemistry in the formation ofmicroporous and mesoporous molecular sievesrdquo Chemistry ofMaterials vol 6 no 10 pp 1816ndash1821 1994
[2] J S Beck J C Vartuli W J Roth et al ldquoA new family of meso-porousmolecular sieves prepared with liquid crystal templatesrdquoJournal of the American Chemical Society vol 114 no 27 pp10834ndash10843 1992
[3] L Giraldo and J C Moreno-Pirajan ldquoCalorimetric study ofmesoporous SBA-15modified for controlled valproic acid deliv-eryrdquo Journal of Chemistry vol 2013 Article ID 267464 11 pages2013
[4] D Halamova M Badanicova V Zelenak T Gondova and UVainio ldquoNaproxen drug delivery using periodic mesoporoussilica SBA-15rdquo Applied Surface Science vol 256 no 22 pp6489ndash6494 2010
[5] J Zhang and J Zhu ldquoA novel amperometric biosensor based ongold nanoparticles-mesoporous silica composite for biosensingglucoserdquo Science in China Series B Chemistry vol 52 no 6 pp815ndash820 2009
[6] Y Park T Kang J Lee P Kim H Kim and J Yi ldquoSingle-steppreparation of Ni catalysts supported on mesoporous silicas(SBA-15 and SBA-16) and the effect of pore structure on theselective hydrodechlorination of 112-trichloroethane to VCMrdquoCatalysis Today vol 97 no 2-3 pp 195ndash203 2004
[7] F-S Xiao ldquoOrdered mesoporous materials with improvedstability and catalytic activityrdquo Topics in Catalysis vol 35 no1-2 pp 9ndash24 2005
[8] G Wirnsberger P Yang B J Scott B F Chmelka and G DStucky ldquoMesostructuredmaterials for optical applications fromlow-k dielectrics to sensors and lasersrdquo SpectrochimicaActa PartA Molecular and Biomolecular Spectroscopy vol 57 no 10 pp2049ndash2060 2001
[9] X Wang and H Yang ldquoA dansyl group modified SBA-15INHIBIT logic gate with [Hg2+ and Clminus] or [Hg2+ and Brminus] asinputsrdquo Applied Surface Science vol 277 pp 257ndash262 2013
[10] L Laskowski and M Laskowska ldquoFunctionalization of SBA-15mesoporous silica by Cu-phosphonate units probing of synthe-sis routerdquo Journal of Solid State Chemistry vol 220 pp 221ndash2262014
[11] J P Ruparelia A K Chatterjee S P Duttagupta and SMukherji ldquoStrain specificity in antimicrobial activity of silverand copper nanoparticlesrdquo Acta Biomaterialia vol 4 no 3 pp707ndash716 2008
[12] L Argueta-Figueroa R A Morales-Luckie R J Scougall-Vilchis and O F Olea-Mejıa ldquoSynthesis characterization andantibacterial activity of copper nickel and bimetallic CundashNinanoparticles for potential use in dental materialsrdquo Progress inNatural Science Materials International vol 24 no 4 pp 321ndash328 2014
[13] M Laskowska L Laskowski K Fijałkowski and M KacprzakldquoSynteza i własciwosci fizykochemiczne krzemionki typu SBA-15 aktywowanej jonamimiedzirdquo InzynieriaMateriałowa vol 35no 6 pp 516ndash518 2014
[14] H Blom R Yeh R Wojnarowski and M Ling ldquoDetection ofdegradation of ABS materials via DSCrdquo Thermochimica Actavol 442 no 1-2 pp 64ndash66 A collection of papers from the 32ndConference ofNorthAmericanThermal Analysis Society 2006
[15] A Gnatowski and J Koszkul ldquoInvestigations of the influenceof compatibilizer and filler type on the properties of chosenpolymer blendsrdquo Journal ofMaterials Processing Technology vol162-163 pp 52ndash58 2005
[16] A Gnatowski and J Koszkul ldquoInvestigation on PAPP mixtureproperties by means of DMTA methodrdquo Journal of MaterialsProcessing Technology vol 175 no 1ndash3 pp 212ndash217 2006
8 Journal of Nanomaterials
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
Figure 5 Structures observed on optical microscope with the magnification 350x (a) PE-HD (b) PE-HD05modifier and (c) PE-HD1modifier
75632
58641 55874
3210
10
20
30
40
50
60
70
80
Ligh
tnes
s (cd
m2)
Figure 6The lightness 119871 of the examined polymer materials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1 modifier
4 Conclusion
We observed influence of active SBA-15 silica filler onmechanical properties of high density polyethylene Adding05 and 1 of copper-containing modifier significantlydiminished1198641015840modulus valueThis divergence varies depend-ing on temperature In the same time the loss angle tangentseems to have similar graph for pure HDPE and modifiedmaterial The only difference is in slight shift of maximum
0 1 2 3
minus1095
minus1916
minus7437
minus1
minus2
minus3
minus4
minus5
minus6
minus7
minus8
ldquoardquo c
oord
inat
e
Figure 7 The value of 119886 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
losses in the case of modified sample Material containing 1of modifier has better dumping properties than pure HDPE
DSC research showed that adding of silica modifiersignificantly decreases crystallinity of the polyethylene whilemaximum temperature of melting and crystallization staysunchanged Nevertheless after adding filler the range ofmelting and crystallization temperature was narrowed
The colour of the modified samples changed significantlyAfter adding copper-containing silica modifier samples
Journal of Nanomaterials 7
27742
21636
0
5
10
15
20
25
30
12 3
minus5
minus10
ldquobrdquo c
oord
inat
e
minus3482
Figure 8 The value of 119887 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
2504
1300
897
0
5
10
15
20
25
30
Glo
ss
1 2 3
Figure 9 Gloss of the examined polymer materials 1 PE-HD 2PE-HD05 modifier and 3 PE-HD1 modifier
become green with colour saturation depending on the fillercontents Also the gloss of the material changed as aresult of modification With increasing modifier contents weobserved decreasing HDPE gloss
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
Financial support for this investigation has been providedby the National Centre of Science (Grant no 201103DST505996)
References
[1] J S Beck J C Vartuli G J Kennedy C T Kresge W J Rothand S E Schramm ldquoMolecular or supramolecular templatingdefining the role of surfactant chemistry in the formation ofmicroporous and mesoporous molecular sievesrdquo Chemistry ofMaterials vol 6 no 10 pp 1816ndash1821 1994
[2] J S Beck J C Vartuli W J Roth et al ldquoA new family of meso-porousmolecular sieves prepared with liquid crystal templatesrdquoJournal of the American Chemical Society vol 114 no 27 pp10834ndash10843 1992
[3] L Giraldo and J C Moreno-Pirajan ldquoCalorimetric study ofmesoporous SBA-15modified for controlled valproic acid deliv-eryrdquo Journal of Chemistry vol 2013 Article ID 267464 11 pages2013
[4] D Halamova M Badanicova V Zelenak T Gondova and UVainio ldquoNaproxen drug delivery using periodic mesoporoussilica SBA-15rdquo Applied Surface Science vol 256 no 22 pp6489ndash6494 2010
[5] J Zhang and J Zhu ldquoA novel amperometric biosensor based ongold nanoparticles-mesoporous silica composite for biosensingglucoserdquo Science in China Series B Chemistry vol 52 no 6 pp815ndash820 2009
[6] Y Park T Kang J Lee P Kim H Kim and J Yi ldquoSingle-steppreparation of Ni catalysts supported on mesoporous silicas(SBA-15 and SBA-16) and the effect of pore structure on theselective hydrodechlorination of 112-trichloroethane to VCMrdquoCatalysis Today vol 97 no 2-3 pp 195ndash203 2004
[7] F-S Xiao ldquoOrdered mesoporous materials with improvedstability and catalytic activityrdquo Topics in Catalysis vol 35 no1-2 pp 9ndash24 2005
[8] G Wirnsberger P Yang B J Scott B F Chmelka and G DStucky ldquoMesostructuredmaterials for optical applications fromlow-k dielectrics to sensors and lasersrdquo SpectrochimicaActa PartA Molecular and Biomolecular Spectroscopy vol 57 no 10 pp2049ndash2060 2001
[9] X Wang and H Yang ldquoA dansyl group modified SBA-15INHIBIT logic gate with [Hg2+ and Clminus] or [Hg2+ and Brminus] asinputsrdquo Applied Surface Science vol 277 pp 257ndash262 2013
[10] L Laskowski and M Laskowska ldquoFunctionalization of SBA-15mesoporous silica by Cu-phosphonate units probing of synthe-sis routerdquo Journal of Solid State Chemistry vol 220 pp 221ndash2262014
[11] J P Ruparelia A K Chatterjee S P Duttagupta and SMukherji ldquoStrain specificity in antimicrobial activity of silverand copper nanoparticlesrdquo Acta Biomaterialia vol 4 no 3 pp707ndash716 2008
[12] L Argueta-Figueroa R A Morales-Luckie R J Scougall-Vilchis and O F Olea-Mejıa ldquoSynthesis characterization andantibacterial activity of copper nickel and bimetallic CundashNinanoparticles for potential use in dental materialsrdquo Progress inNatural Science Materials International vol 24 no 4 pp 321ndash328 2014
[13] M Laskowska L Laskowski K Fijałkowski and M KacprzakldquoSynteza i własciwosci fizykochemiczne krzemionki typu SBA-15 aktywowanej jonamimiedzirdquo InzynieriaMateriałowa vol 35no 6 pp 516ndash518 2014
[14] H Blom R Yeh R Wojnarowski and M Ling ldquoDetection ofdegradation of ABS materials via DSCrdquo Thermochimica Actavol 442 no 1-2 pp 64ndash66 A collection of papers from the 32ndConference ofNorthAmericanThermal Analysis Society 2006
[15] A Gnatowski and J Koszkul ldquoInvestigations of the influenceof compatibilizer and filler type on the properties of chosenpolymer blendsrdquo Journal ofMaterials Processing Technology vol162-163 pp 52ndash58 2005
[16] A Gnatowski and J Koszkul ldquoInvestigation on PAPP mixtureproperties by means of DMTA methodrdquo Journal of MaterialsProcessing Technology vol 175 no 1ndash3 pp 212ndash217 2006
8 Journal of Nanomaterials
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
Figure 8 The value of 119887 coordinate for the examined polymermaterials 1 PE-HD 2 PE-HD05 modifier and 3 PE-HD1modifier
2504
1300
897
0
5
10
15
20
25
30
Glo
ss
1 2 3
Figure 9 Gloss of the examined polymer materials 1 PE-HD 2PE-HD05 modifier and 3 PE-HD1 modifier
become green with colour saturation depending on the fillercontents Also the gloss of the material changed as aresult of modification With increasing modifier contents weobserved decreasing HDPE gloss
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
Financial support for this investigation has been providedby the National Centre of Science (Grant no 201103DST505996)
References
[1] J S Beck J C Vartuli G J Kennedy C T Kresge W J Rothand S E Schramm ldquoMolecular or supramolecular templatingdefining the role of surfactant chemistry in the formation ofmicroporous and mesoporous molecular sievesrdquo Chemistry ofMaterials vol 6 no 10 pp 1816ndash1821 1994
[2] J S Beck J C Vartuli W J Roth et al ldquoA new family of meso-porousmolecular sieves prepared with liquid crystal templatesrdquoJournal of the American Chemical Society vol 114 no 27 pp10834ndash10843 1992
[3] L Giraldo and J C Moreno-Pirajan ldquoCalorimetric study ofmesoporous SBA-15modified for controlled valproic acid deliv-eryrdquo Journal of Chemistry vol 2013 Article ID 267464 11 pages2013
[4] D Halamova M Badanicova V Zelenak T Gondova and UVainio ldquoNaproxen drug delivery using periodic mesoporoussilica SBA-15rdquo Applied Surface Science vol 256 no 22 pp6489ndash6494 2010
[5] J Zhang and J Zhu ldquoA novel amperometric biosensor based ongold nanoparticles-mesoporous silica composite for biosensingglucoserdquo Science in China Series B Chemistry vol 52 no 6 pp815ndash820 2009
[6] Y Park T Kang J Lee P Kim H Kim and J Yi ldquoSingle-steppreparation of Ni catalysts supported on mesoporous silicas(SBA-15 and SBA-16) and the effect of pore structure on theselective hydrodechlorination of 112-trichloroethane to VCMrdquoCatalysis Today vol 97 no 2-3 pp 195ndash203 2004
[7] F-S Xiao ldquoOrdered mesoporous materials with improvedstability and catalytic activityrdquo Topics in Catalysis vol 35 no1-2 pp 9ndash24 2005
[8] G Wirnsberger P Yang B J Scott B F Chmelka and G DStucky ldquoMesostructuredmaterials for optical applications fromlow-k dielectrics to sensors and lasersrdquo SpectrochimicaActa PartA Molecular and Biomolecular Spectroscopy vol 57 no 10 pp2049ndash2060 2001
[9] X Wang and H Yang ldquoA dansyl group modified SBA-15INHIBIT logic gate with [Hg2+ and Clminus] or [Hg2+ and Brminus] asinputsrdquo Applied Surface Science vol 277 pp 257ndash262 2013
[10] L Laskowski and M Laskowska ldquoFunctionalization of SBA-15mesoporous silica by Cu-phosphonate units probing of synthe-sis routerdquo Journal of Solid State Chemistry vol 220 pp 221ndash2262014
[11] J P Ruparelia A K Chatterjee S P Duttagupta and SMukherji ldquoStrain specificity in antimicrobial activity of silverand copper nanoparticlesrdquo Acta Biomaterialia vol 4 no 3 pp707ndash716 2008
[12] L Argueta-Figueroa R A Morales-Luckie R J Scougall-Vilchis and O F Olea-Mejıa ldquoSynthesis characterization andantibacterial activity of copper nickel and bimetallic CundashNinanoparticles for potential use in dental materialsrdquo Progress inNatural Science Materials International vol 24 no 4 pp 321ndash328 2014
[13] M Laskowska L Laskowski K Fijałkowski and M KacprzakldquoSynteza i własciwosci fizykochemiczne krzemionki typu SBA-15 aktywowanej jonamimiedzirdquo InzynieriaMateriałowa vol 35no 6 pp 516ndash518 2014
[14] H Blom R Yeh R Wojnarowski and M Ling ldquoDetection ofdegradation of ABS materials via DSCrdquo Thermochimica Actavol 442 no 1-2 pp 64ndash66 A collection of papers from the 32ndConference ofNorthAmericanThermal Analysis Society 2006
[15] A Gnatowski and J Koszkul ldquoInvestigations of the influenceof compatibilizer and filler type on the properties of chosenpolymer blendsrdquo Journal ofMaterials Processing Technology vol162-163 pp 52ndash58 2005
[16] A Gnatowski and J Koszkul ldquoInvestigation on PAPP mixtureproperties by means of DMTA methodrdquo Journal of MaterialsProcessing Technology vol 175 no 1ndash3 pp 212ndash217 2006
8 Journal of Nanomaterials
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
[17] K P Pramoda and T Liu ldquoEffect of moisture on the dynamicmechanical relaxation of polyamide-6clay nanocompositesrdquoJournal of Polymer Science Part B Polymer Physics vol 42 no10 pp 1823ndash1830 2004
[18] M Maity B B Khatua and C K Das ldquoEffect of processing onthe thermal stability of the blends based on polyurethane partIVrdquo Polymer Degradation and Stability vol 72 no 3 pp 499ndash503 2001
[19] A Gnatowski ldquoInfluence of the polyvinylpyrrolidone modifi-cation on crystallines and properties of selected thermoplasticpolymersrdquo Journal of Polymer Engineering vol 27 no 6-7 pp507ndash524 2007
[20] T D Papathanasiou and M R Kamal ldquoFilling of a complex-shaped mold with a viscoelastic polymer Part I the mathemat-ical modelrdquo Polymer Engineering amp Science vol 33 no 7 pp400ndash409 1993
[21] M S Perera U Ishiaku and Z M Ishak ldquoCharacterisation ofPVCNBR and PVCENR50 binary blends and PVCENR50NBR ternary blends by DMA and solid state NMRrdquo EuropeanPolymer Journal vol 37 no 1 pp 167ndash178 2001
[22] R E Wetton ldquoDynamic mechanical method in the character-isation of solid polymersrdquo Polymer Testing vol 4 no 2ndash4 pp117ndash129 1984
[24] B Wunderlich ldquoReversible crystallization and the rigidndashamor-phous phase in semicrystalline macromoleculesrdquo Progress inPolymer Science vol 28 no 3 pp 383ndash450 2003
[25] S S Ray andM Okamoto ldquoPolymerlayered silicate nanocom-posites a review from preparation to processingrdquo Progress inPolymer Science vol 28 no 11 pp 1539ndash1641 2003
