bioactive glass particulate filler composite

8
d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570–577 Available online at www.sciencedirect.com ScienceDirect jo ur nal ho me pag e: www.intl.elsevierhealth.com/journals/dema Bioactive glass particulate filler composite: Effect of coupling of fillers and filler loading on some physical properties Onur Oral a,, Lippo V. Lassila a , Ovul Kumbuloglu b , Pekka K. Vallittu a a Department of Biomaterials Science & Turku Clinical Biomaterials Centre—TCBC, Institute of Dentistry, University of Turku, Lemminkäisenkatu 2, FI-20014 Turku, Finland b Department of Prosthodontics, Faculty of Dentistry, Ege University, Izmir, Turkey a r t i c l e i n f o Article history: Received 16 April 2013 Accepted 20 February 2014 Keywords: Bioactive glass Biostable glass Silanization Polymers Composite Biopolymer a b s t r a c t Objectives. The aim of this study was to investigate the effect of silanization of biostable and bioactive glass fillers in a polymer matrix on some of the physical properties of the composite. Methods. The water absorption, solubility, flexural strength, flexural modulus and toughness of different particulate filler composite resins were studied in vitro. Five different speci- men groups were analyzed: A glass-free control, a non-silanized bioactive glass, a silanized bioactive glass, a non-silanized biostable glass and a silanized biostable glass groups. All of these five groups were further divided into sub-groups of dry and water-stored materi- als, both of them containing groups with 3 wt%, 6 wt%, 9 wt% or 12 wt% of glass particles (n = 8 per group). The silanization of the glass particles was carried out with 2% of gamma- 3-methacryloxyproyltrimethoxysilane (MPS). For the water absorption and solubility tests, the test specimens were stored in water for 60 days, and the percentages of weight change were statistically analyzed. Flexural strength, flexural modulus and toughness values were tested with a three-point bending test and statistically analyzed. Results. Higher solubility values were observed in non-silanized glass in proportion to the percentage of glass particles. Silanization, on the other hand, decreased the solubility values of both types of glass particles and polymer. While 12 wt% non-silanized bioactive glass specimens showed 0.98 wt% solubility, 12 wt% silanized biostable glass specimens were observed to have only 0.34 wt% solubility. The three-point bending results of the dry specimens showed that flexural strength, toughness and flexural modulus decreased in proportion to the increase of glass fillers. The control group presented the highest results (106.6 MPa for flexural strength, 335.7 kPA for toughness, 3.23 GPa for flexural modulus), whereas for flexural strength and toughness, 12 wt% of non-silanized biostable glass filler groups presented the lowest (70.3 MPa for flex- ural strength, 111.5 kPa for toughness). For flexural modulus on the other hand, 12 wt% of silanized biostable glass filler group gave the lowest results (2.57 GPa). Corresponding author. Tel.: +90 553 2175103; fax: +90 232 2274053/2273420. E-mail address: onuora@utu.fi (O. Oral). http://dx.doi.org/10.1016/j.dental.2014.02.017 0109-5641/Crown Copyright © 2014 Published by Elsevier Ltd on behalf of The Academy of Dental Materials. All rights reserved.

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  • d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

    Available online at www.sciencedirect.com

    ScienceDirect

    jo ur nal ho me pag e: www.int l .e lsev ierhea l th .com/ journa ls /dema

    Bioac posite: Effect ofcoupling of llers and ller loading on somephysical properties

    Onur Ora Departmenof Turku, Leb Departmen

    a r t i c

    Article histor

    Received 16

    Accepted 20

    Keywords:

    Bioactive gl

    Biostable gl

    Silanization

    Polymers

    Composite

    Biopolymer

    CorrespoE-mail a

    http://dx.do0109-5641/Cala,, Lippo V. Lassilaa, Ovul Kumbuloglub, Pekka K. Vallittua

    t of Biomaterials Science & Turku Clinical Biomaterials CentreTCBC, Institute of Dentistry, Universitymminkisenkatu 2, FI-20014 Turku, Finlandt of Prosthodontics, Faculty of Dentistry, Ege University, Izmir, Turkey

    l e i n f o

    y:

    April 2013

    February 2014

    ass

    ass

    a b s t r a c t

    Objectives. The aim of this study was to investigate the effect of silanization of biostable

    and bioactive glass llers in a polymer matrix on some of the physical properties of the

    composite.

    Methods. The water absorption, solubility, exural strength, exural modulus and toughness

    of different particulate ller composite resins were studied in vitro. Five different speci-

    men groups were analyzed: A glass-free control, a non-silanized bioactive glass, a silanized

    bioactive glass, a non-silanized biostable glass and a silanized biostable glass groups. All

    of these ve groups were further divided into sub-groups of dry and water-stored materi-

    als, both of them containing groups with 3 wt%, 6 wt%, 9 wt% or 12 wt% of glass particles

    (n = 8 per group). The silanization of the glass particles was carried out with 2% of gamma-

    3-methacryloxyproyltrimethoxysilane (MPS). For the water absorption and solubility tests,

    the test specimens were stored in water for 60 days, and the percentages of weight change

    were statistically analyzed. Flexural strength, exural modulus and toughness values were

    tested with a three-point bending test and statistically analyzed.

    Results. Higher solubility values were observed in non-silanized glass in proportion to the

    percentage of glass particles. Silanization, on the other hand, decreased the solubility values

    of both types of glass particles and polymer. While 12 wt% non-silanized bioactive glass

    specimens showed 0.98 wt% solubility, 12 wt% silanized biostable glass specimens wereobserved to have only 0.34 wt% solubility.

    The three-point bending results of the dry specimens showed that exural strength,

    toughness and exural modulus decreased in proportion to the increase of glass llers.

    The control group presented the highest results (106.6 MPa for exural strength, 335.7 kPA

    for toughness, 3.23 GPa for exural modulus), whereas for exural strength and toughness,

    12 wt% of non-silanized biostable glass ller groups presented the lowest (70.3 MPa for ex-

    ural strength, 111.5 kPa for toughness). For exural modulus on the other hand, 12 wt% of

    silanized biostable glass ller group gave the lowest results (2.57 GPa).

    nding author. Tel.: +90 553 2175103; fax: +90 232 2274053/2273420.ddress: onuora@utu. (O. Oral).

    i.org/10.1016/j.dental.2014.02.017rown Copyright 2014 Published by Elsevier Ltd on behalf of The Academy of Dental Materials. All rights reserved.tive glass particulate ller com

  • d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577 571

    Signicance. The silanization of glass llers improved the properties of the glass as well as

    the properties of the composite. Silanization of bioactive glass may protect the glass from

    leaching at early stage of water storage.

    lishe

    1. Int

    Synthetic hceramics haimplants mtive matersystem, Bimodied bythe eld of position of presently Bity and antprominent through ththe subseqCaP, in shprocess, abioactivity

    Both bioas biomatemethacrylamer used fPMMA haslong bone simplants [1ever, is impthe ller paout of the mto the propSilanes as ticles to thbiostable orprovide proerties of thtime. Gamthe silane the most st

    The aimcal charactbiostable glof the glass

    2. Ma

    The resin son an autoglycol dimpowder coWehrheim,1000 m, V

    lar silanisites

    BG of pded

    9 wtes ws: 2 wr thes ofAldrer. Th to ried

    gla mmerizationre, 1, Lieby 1s A/

    spnesslled bept iwereecim

    wared b

    immight emovnd w

    (0.00 wertion

    bsor

    tial w (g).

    meCrown Copyright 2014 Pub

    roduction

    ydroxyapatites, bioactive glass (BG) and glass-ve been used in recent years to transform biostableade of metals and polymer composites into bioac-ials [15]. After the introduction of the rst BGoglass45S5 by Prof. Hench, the system has been

    many researchers, and it has been introduced totissue engineering [6,7]. Modications to the com-BG were undertaken by Andersson et al. [8,9], andG S53P4 is used in applications where bioactiv-imicrobial properties are required [10]. The mostfeature of BGs is their bioactivity. Bioactivity occurse union of calcium and phosphate groups anduent formation of a calcium phosphate (CaO-P2O5,ort) layer. CaP formation is a tissue-dependentnd in vitro bioactivity correlates with in vivo[10,11].degradable and biostable polymers are used widelyrials in medicine and dentistry [1214]. Poly(methylte) (PMMA) is a commonly used biostable poly-or example in bone cements and dentures [1518].

    been combined with BG llers to be used asegmental defect repair materials and in calvarial921]. Adhesion between ller and polymer, how-ortant in the transfer of load from the matrix torticles. The BG ller particles, as they are leachedatrix over time, could cause considerable changeserties of the composite under moist conditions.bi-functional compounds can bind the ller par-e polymer matrix regardless whether the glass is

    leachable. In the latter case, silanization may alsotection for leaching, and thus the mechanical prop-e composite may be retained for a longer period ofma-3-methacryloxypropyltrimethoxysilane (MPS),used in this study, is a trialkoxysilane and one ofudied silane compounds [2225].

    of the study was to evaluate some of the physi-eristics composites containing both bioactive andass with regard to the silanization and ller loading.

    terials and methods

    (granuboth scompo

    Thethe aidand ad6 wt%,particlfollowand foof glasSigmadecantfor 24 then d

    Theinto 65polyminstrucpressuSchaandown (Struer300 rpma thickcontrothen kmens test sp

    Themeasubeforethe wewere rdried a0.1 mgvaluesabsorpbelow:

    Water a

    m1: iniweight

    The

    ystem for the matrix of the composites was basedpolymerizing methyl methacrylate and ethyleneethacrylate (95:5, w/w) monomer system with amponent of PMMA (Palapress, Heraeus-Kulzer,

    Germany). Bioactive (particulate size from 315 toivoxid LTD., Finland) and biostable glass particles

    sured by atesting mawere placedtip on the sof the deviFlexural strd by Elsevier Ltd on behalf of The Academy of Dental

    Materials. All rights reserved.

    ize from 915 to 1000 m, Vivoxid LTD., Finland),zed and non-silanized, were used as llers in the

    (Table 1).and biostable glass particles were measured withrecision scale of 1 mg (Mettler PM100, Toledo, USA)

    to the resin in PMMA powder to prepare 3 wt%,%, and 12 wt% composites. Silanization of glassas done before adding them in to the resin ast% MPS-silane (98% MPS, lot.0182EH-497, Aldrich)

    hydrolysis of the MPS-silane, double the amount toluene (99.5%, A.C.S reagent lot.03334ME-157,ich) were mixed with the glass particles in ahe silanization decanter was left in a fume hoodevaporate the toluene, and the glass powder wasin 90 C for 3 h.ss particle containing resin mixture was poured

    10 mm 3.5 mm stainless steel molds and thetion was carried out according to manufacturerss (10 mL powder/7 mL liquid; under 55 C, 200 kPa5 min curing time) (Ivomat, Typ IP 2, Ivoclar AG.,chtenstein). Polymerized specimens were ground80, 500, 1200-grit (FEPA) silicon carbide papersS, Rodovre, Denmark) under water cooling witheed (LaboPol-21, Struers A/S, Rodovre, Denmark) to

    of 3 0.1 mm. The specimens dimensions werey the means of an electronic caliper, and they weren excicator for 1 week before testing. Test speci-

    classied as shown in Table 2. There were eightens (n = 8) in each of the groups.ter absorption of the composite specimens wasy determining the initial weights of the specimensersion (m1) to distilled water and comparing it withof the specimen after immersion (m2). Specimensed from water on days of 1, 2, 3, 7, 14, 21, 30, 45, 60;eighed after 1 min by the aid of precision scale of01 g) (Mettler Toledo AT261 DeltaRang, USA). Tene obtained in this way from each specimen. Water

    percentages were determined using the formula

    ption% = m2 m1m1

    100

    eight before absorption test (g); m2: last measured

    chanical properties of the specimens were mea-

    three point bending test performed by universalchine (Lloyd LRX Plus, United Kingdom). Samples

    on supports 50 mm apart, and the force applyingample in the middle of the two supports. The speedce was set at 5 1 mm/min till fracture occurred.ength, exural modulus and toughness data were

  • 572 d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

    Table 1 Compositions of glasses used in the study.

    Product nufa

    BG particu xid L

    Biostable gparticula

    xid L

    Table 2

    Group

    Control groC-d C-w

    Non-silaniBS3-ns-d BS3-ns-w BS6-ns-d BS6-ns-w BS9-ns-d BS9-ns-w BS12-ns-d BS12-ns-w

    Silanized bBS3-s-d BS3-s-w BS6-s-d BS6-s-w BS9-s-d BS9-s-w BS12-s-d BS12-s-w

    Non-silaniBG3-ns-d BG3-ns-w BG6-ns-d BG6-ns-w BG9-ns-d BG9-ns-w BG12-ns-d BG12-ns-w

    Silanized bBG3-s-d BG3-s-w BG6-s-d BG6-s-w BG9-s-d BG9-s-w BG12-s-d BG12-s-w

    determinedtion of stre

    T.S. = 3 2 b

    T.S.: exure (N), l: di(mm); h: sa

    Y.M. = StreStra

    Y.M.: Fleat time of fDescription Ma

    lates S53P4 glass system, particulate size3151000 m

    Vivo

    lasstes

    Particulate size 9151000 m Vivo

    Description of test groups used in this study (n = 8/group).

    Storage

    upsDry In water, 60 days

    zed biostable glass ller groupsDry

    In water, 60 days Dry In water, 60 days Dry In water, 60 days Dry

    In water, 60 days

    iostable glass ller groupsDry In water, 60 days Dry In water, 60 days Dry In water, 60 days Dry In water, 60 days

    zed bioactive glass ller groupsDry In water, 60 days Dry In water, 60 days Dry In water, 60 days Dry

    In water, 60 days

    ioactive glass ller groupsDry In water, 60 days Dry In water, 60 days Dry In water, 60 days Dry In water, 60 days

    as previously [13,14,2629]. Formulas for calcula-ngth, modulus of elasticity and toughness were:

    F L h2

    ural strength (N/mm2 = MPa); F: load at time of fail-stance between the supports (mm); b: sample widthmple thickness (mm).

    ss

    in= P l

    3

    4 b h3 dxural modulus (N/mm2, MN/m2, MPa, GPa); P: loadailure (N); l: distance between the supports (mm);

    b: sample wbending va

    Toughness =

    Toughnessamount of

    Solubilitabsorptionmass loss aposites werby rst weigfor nine dacturer Composition

    td., Turku, Finland SiO2 53 wt%, Na2O 23 wt%,CaO 20 wt% and P2O5 4 wt%

    td., Turku, Finland SiO2 70 wt%, Na2O 17 wt%and CaO 13 wt%

    Description

    Control, no llersControl, no llers

    Biostable glass, 3%-wt, not silanized

    Biostable glass, 3%-wt, not silanizedBiostable glass, 6%-wt, not silanizedBiostable glass, 6%-wt, not silanizedBiostable glass, 9%-wt, not silanizedBiostable glass, 9%-wt, not silanizedBiostable glass, 12%-wt, not silanizedBiostable glass, 12%-wt, not silanized

    Biostable glass, 3%-wt, silanizedBiostable glass, 3%-wt, silanizedBiostable glass, 6%-wt, silanizedBiostable glass, 6%-wt, silanizedBiostable glass, 9%-wt, silanizedBiostable glass, 9%-wt, silanizedBiostable glass, 12%-wt, silanizedBiostable glass, 12%-wt, silanized

    Bioactive glass, 3%-wt, not silanizedBioactive glass, 3%-wt, not silanizedBioactive glass, 6%-wt, not silanizedBioactive glass, 6%-wt, not silanizedBioactive glass, 9%-wt, not silanizedBioactive glass, 9%-wt, not silanizedBioactive glass, 12%-wt, not silanizedBioactive glass, 12%-wt, not silanized

    Bioactive glass, 3%-wt, silanizedBioactive glass, 3%-wt, silanizedBioactive glass, 6%-wt, silanizedBioactive glass, 6%-wt, silanizedBioactive glass, 9%-wt, silanizedBioactive glass, 9%-wt, silanizedBioactive glass, 12%-wt, silanizedBioactive glass, 12%-wt, silanized

    idth (mm); h: sample thickness (mm); d: highestlue (mm). f

    0

    d

    (J/m3, N/m2, MN/m3, MPa); : amount of strain; f:stress at time of failure; : amount of stress.y percentages were obtained by subtracting the

    percentages of the specimens from percentages offter drying. The mass loss percentages of the com-e tested immediately after three-point bending testhing the specimens wet (m3) and then drying themys at 80 C and weighing again (m4). The weights

  • d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577 573

    BS3-n s-w

    BS6-n s-w

    BS9-ns-w

    BS12- ns-w

    BS3-s-w

    BS6-s- w BS9-s-w

    BS12-s-w

    BG3-ns-w

    BG3-s- w

    BG6-s- w

    BG9-s-w

    BG12-s-wC-w

    1.2

    1.25

    1.3

    1.35

    1.4

    1.45

    1.5

    1.55

    1.6

    1.65

    1.7

    1.75

    1.8

    1.85

    D

    wt-

    % W

    ater

    abs

    orp

    on b

    y da

    y

    Fig. 1

    of the specrm they hsamples we

    Mass loss%

    m3: initial wweight (g).

    Solubility percentages were calculated using the followingformula:

    (Solubility%) = (Mass loss%) (Water absorption%)

    Statistical analysis was carried out with SPSS 15.0 forWindows (SPSS Inc., Chicago, USA) package program. Waterabsorption results were evaluated by Shapiro-Wilk test todemonstrate normal distribution of the data. Differencesbetween groups were evaluated by one-way ANOVA and Dun-nett T3 test (p < 0.05). Solubility, exural strength, exuralmodulus, toughness results were evaluated by Shapiro-Wilk.Differences between groups were evaluated by KruskalWallisand MannWhitney tests (p < 0.05).

    3. Results

    The water absorption of composites is presented in and 2, and weight gain in relation to storage time inin Figabsod BGller

    e torouproupl groBG6-ns-w

    BG9-ns-w

    BG12- ns-w

    ay-1 4 Day-2 1 Day-3 0 Day-4 5 Day-60

    BS3- ns-w BS 6-ns-w BS9- ns-w BS 12-n s-wBS3-s -w BS6-s- w BS9-s-w BS12-s- w

    Figs. 1water water wt) anglass ferencller gonly gcontroBG3-ns-w BG6- ns-w BG 9-ns-w BG1 2-n s-wBG3-s- w BG6 -s-w BG 9-s- w BG12-s- wC-w

    Weight gain of specimens in water by day.

    imens were monitored during this period to con-ad dried completely. Mass loss percentages of there then calculated by the formula below:

    =(

    m4 m3m3

    ) 100

    eight before solubility test (g); m4: last measured

    had a tendnon-silanizportions ofstatisticallyweight of twith excepwhich showfor more thvalues for Bday 30. Thewas observBS12-ns-w

    The soluFig. 3. Thens-w (0.98(0.34 0.03

    Fig. 2 Water absorption values of sub-gr. 1. The highest and lowest values observed in therption test were in groups BS12-s-w (1.83 0.04%-12-ns-w (1.21 0.07%-wt). In the non-silanized

    groups, 3%-wt groups showed no signicant dif- the control group (p > 0.05). In silanized glasss, only BG3-s-w and BG6-s-w groups were thes which showed signicant difference to theup (p < 0.05). All in all, water absorption valuesency to decrease with increasing proportions ofed glass ller, and to increase with increasing pro-

    silanized glass ller. These changes were found signicantly different (p < 0.05). Generally, thehe specimens increased during the 60 days periodtion of groups BG6-ns-w, BG9-ns-w, BG12-ns-wed reduction in weight after being stored in wateran 30 days (Fig. 1), and thus, maximum absorptionG6-ns-w and BG9-ns-w groups were observed on

    BG12-ns-w groups highest water absorption valueed on day 21. The BG3-s-w, BG6-s-w, BG9-s-w andgroups peak values were observed on day 45.bilities of the different composites are given in

    highest solubility value was observed in BG12- 0.03%-wt) and the lowest value in BS12-s-w%-wt). Solubility values of biostable glass ller

    oups on day 60.

  • 574 d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

    Fig. 3 Sol

    groups exccomparisonller groupshowed sig(p < 0.05). Aing proportto non-silasignicantl

    Flexuralgroup (Fig. strength thmens, incrstrength. Hshowed sigof the llernicant dif(p > 0.05) (Fi

    Flexuraltion of glasilanizationsilanized g

    Toughnemen groupglass ller ggroups wercontrol gro

    4. Di

    Materials tproperties,ductive or strength, amaterials tites of bioafocused onglass and P

    The cofeatures oftion in unfbetween tattained [3componenparticles w

    Special emphasis in the study was given to the behaviour ofbioactive glass particles in the composites, as they are subject

    olut parter toissosite

    thattive ]. It isted ttion

    to e of for watrixo be al [3able ke coompnerathe p

    on staed ttionals sithohoul

    mated ble gluctuompof was sigs.

    by e p

    polyeneresultred, le, ing of subility percentages of sub-groups on day 60.

    ept BS12-s-w showed no signicant difference in to the control group (p > 0.05). However, in the BG

    s, most sub-groups except BG3-ns-w and BG9-s-wnicant differences compared to the control groups a whole, solubility values decreased with increas-ions of silanized glass and increased in proportionnized BG glass, and these differences were foundy different (p < 0.05).

    strength was found to be highest in the control4), and dry specimens were found to show higheran water stored specimens (p < 0.05). In dry speci-eased quanties of glass llers lowered the exuralowever, only the 12 wt% glass ller sub-groupsnicant differences in wet specimens. Silanizations, on the other hand, was not found to confer a sig-ference to the exular strength of the compositesg. 4).

    modulus was signicantly decreased by the addi-ss llers in all specimens (p < 0.05). The ller

    was observed with lower results than non-roups (Fig. 5).ss was reduced by glass llers in all dry speci-

    s, whereas in wet specimens, only 12%-wt biostableroups showed reduction. Other wet specimen sub-e not signicantly different in comparison to theup (p > 0.05) (Fig. 6).

    scussion

    hat combine biologically and clinically important

    to dissgroupsin ordcles. Dcompoknowna nega[3436is relaabsorprelatedvolumpaths the mhave tmaterivulnercan tatheir ccan ge

    In formedweightobservabsorpmateririals wller stestedsilanizbiostabthe strtion. Cterms tion wller (Fcausedinto thPMMA

    In gtion rmeasuexamploadin such as the capability to provide an osteocon-osteoinductive surface and long term retention ofre desired in bone reconstructions. One group ofhat could provide such properties may be compos-ctive glass and PMMA. Therefore the present study

    the characterization of composites of bioactiveMMA.ncept of hybrid materials utilizing favourable

    different constituent materials proposes a reduc-avourable initial properties. However, integrationhe components of hybrid materials has to be032]. For this purpose, organic and inorganicts were bound reciprocally by coating glass llerith silanol groups by hydrolysis of MPS-silane [33].

    was found the silanizetection of tnetwork. Into have highThis resultposition anglass has abioactive gcations. CaSiOSi linkbridging oxions is dir[10,41,42].ion in aqueous environments. In some compositeicles were coupled to the polymer matrix by silane

    slow down the leaching of the glass ller parti-lution of bioactive glass in the polymer matrix ofis based on water absorption to the matrix. It is

    in immersed solutions high polymer solubility haseffect on the physical properties of the material

    also known that the hydrophobicity of a materialo its water absorption and solubility [37,38]. Water

    in a polymer matrix occurs by diffusion and it isthe amount of ller content, as ller reduces thethe polymer matrix phase and creates potentialater diffusion through the interphases between

    and llers. Thus, water absorption and solubilitystudied in order to understand the properties of a4,39]. Certain biopolymers and bioactive glasses areto water absorption and solubility. These materialsmponents from the immersed solution and leachonents to the liquid. These leached componentste tissue reactions [17,40].resent study, water absorption testing was per-

    cumulative days to receive an understanding ofbilization. In the water absorption test, it washat non-silanized glass ller groups had lower

    than silanized ller groups. Generally, ller loadedhowed lower water absorption than control mate-ut llers. In principle, the group with 12 wt% glassd have had the lowest water absorption of theerials, but this was found only in the case of non-ioactive glass llers. Higher water absorption withass llers may reect the existence of minor gaps inre of the composite, which increase water absorp-arison of silanized and non-silanized llers inater absorption demonstrated that water absorp-lightly higher in the groups with silanized glass1 and 2). This may be due to polysiloxane networkssilanization and the tendency of water to diffuseolysiloxane network more readily than into themer matrix.al, solubility results were opposite to water absorp-s: where lower water absorption values werehigher solubility values were observed, as for

    non-silanized glass ller groups. Increasing theilanized glass llers, both bioactive and biostable,to decrease solubility. The decreasing solubility ind glass ller groups can be attributed to the pro-

    he glass structure by the silane based polysiloxane addition, the bioactive glass groups were observeder solubility than the biostable glass groups (Fig. 3).

    can be associated with the difference of the com-d structure of the two types of glass. Biostable

    tetrahedron structure resistant to reactions, whilelass has a structure more open to reactions withtions in bioactive glass disrupt the continuity ofs and this process results with formation of non-ygen ions. The amount of non-bridging oxygen

    ectly related to the bioactivity of bioactive glass

  • d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577 575

    Fig. 4 Flexural strength values of sub-groups on day 60.

    Discontinuity and stress transfer interruption in the mainmatrix by cles by visca stronger been reporpolymer isreduces theof the glassbe reduced

    The longcal propertmost impociently reinFillers of hibetter reinfllers [45]. strength anlus in dry sto the featwere foundenvironme

    Test specimens were subjected to a three-point bendingmediately after the conclusion of the absorption test.ing ymerntai4.8 Mer, nally lnda

    werich hts

    akenhe lationn thbrid

    otheter d

    proolylaller particles was prevented by saturating the parti-ous acrylate using silane coupling agents to providebond between the substrate and ller [36]. It hasted that the polymerization and structure of the

    not affected by MPS-silane [43]. In fact, silane amount of monomer required for the saturation

    ller. Thus, the adverse effects of monomers can [44].-term function of a material depends on its physi-

    ies, of which load-bearing capacity is clinically thertant. Particulate llers in composites do not ef-force a material against bending and tensile forces.gher aspect ratio, namely bers, have considerablyorcing and toughening capabilities than particulateFrom this perspective the decrease of transversed toughness and the increase of transverse modu-pecimen groups were what was to be expected dueures of glass llers. However, polymer properties

    to have no change when immersed in an aqueousnt (Figs. 46).

    test imAccordof polples coand 10HowevespeciISO staimenstest whin weigwere t

    In timplicagree oand hyon thebe bettissuesthat pFig. 5 Flexural modulus values of sub-grto ISO 1567:1999 standards, transversal strengths must be at least 65 MPa. In our study, sam-ning glass as llers showed values between 70.3Pa, which is sufcient for ISO standards (Fig. 4).ovel composite materials for clinical applications,eachable llers, cannot necessarily be judged byrds. After the three-point bending test the spec-e placed back in their solutions for the solubilitywas carried out the same day. Percentage changesdue to material loss in the three-point bending test

    into consideration in the solubility calculations.iterature, there are various interpretations of thes of materials modied by glass llers. Researcherse course of the physical degradation of polylactidspolylactid materials with BG ller in vitro [36,46,47];r hand, in vivo physical properties were found toue to bioactivity and enhanced bonding to livingmoted by BGs [48]. Likewise, it has been statedctids containing BG coupledby MPS-silane conferoups on day 60.

  • 576 d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

    roup

    improved stivity propematerials hand not be irial containincrease thtion of bethe particu

    In this sticles was compared tsilanes ma

    5. Co

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    1. Accordinubility tin non-glass llsame tiever, soboth bio

    2. Dry comwith incpropertiincreasi

    3. The couthe resicaused leaching

    Acknowl

    This researInternationBiomateriaresearch is

    m (w and Profed foked

    r e n

    llo Aarhi Toactiater Moritzaracbstraed 20oritzplan

    udy. usa ne dmpoater Rssi SFig. 6 Toughness values of sub-g

    trength, osteoblastic activation and osteoconduc-rties in vivo [49]. According to our ndings, hybridave to be applied carefully until bioactivity occurs,mplanted on load-bearing areas if the hybrid mate-s over 12%-wt of glass ller. One alternative toe strength of the composite could be the utiliza-r reinforcements of high aspect ratio to reinforcelate ller composite [10].tudy, the modication of polymers by glass par-investigated in vitro. Next, our ndings should beo in vivo results and investigate more in detail howy alter bioactivity of the bioactive glass.

    nclusion

    ndings obtained in this study are as follows:

    g to the results of the water absorption and sol-ests, the highest water absorption was observedsilanized BG groups. Increasing the amount ofer loading decreased water absorption while at theme increasing solubility. After silanization, how-

    PrograAlfontTCBC. thankeis than

    r e f e

    [1] BaNbiM

    [2] MChsuM

    [3] MImst

    [4] TubocoM

    [5] Ro

    lubility decreased with increasing proportions ofactive and biostable glass.posite specimens showed lower physical valuesreasing glass ller loading, whereas the exurales of water-stored specimens did not alter withng glass proportions.pling of glass ller particles with silane improvesstance of the composite resin against weakeningwater and may protect bioactive glass llers from.

    edgements

    ch was nancially supported by CIMO (Centre foral Mobility) and it was carried out in Turku Clinicalls Centre - TCBC, University of Turku, Finland. This

    part of the BioCity Turku Biomaterials Research

    Comparutile-sBiomed

    [6] LindforKankargraft su2010;47

    [7] WilsonLL, WilSingap

    [8] AndersTurku,

    [9] AndersJ, JuhanSiO2-NMed 19

    [10] Zhang thesis.

    [11] Ngangaporouss on day 60.

    ww.biomaterials.utu.). Minttu Vigren, GenevieveHanna Mark are thanked for their help with tests inssor Jukka Matinlinna (University of Hong Kong) is

    r sharing his silane studies with us. Timothy Wilsonfor proofreading the manuscript.

    c e s

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    Bioactive glass particulate filler composite: Effect of coupling of fillers and filler loading on some physical properties1 Introduction2 Materials and methods3 Results4 Discussion5 ConclusionAcknowledgementsReferences