当前位置：文档库 › Zr掺杂铁硼磷酸盐玻璃的结构分析

Zr掺杂铁硼磷酸盐玻璃的结构分析

The crystallization and FTIR spectra of ZrO 2-doped

36Fe 2O 3–10B 2O 3–54P 2O 5glasses and crystalline

compounds

Fu Wang a ,Qilong Liao a ,?,Kuiru Chen a ,Sheqi Pan b ,Mingwei Lu a

a State Key Laboratory Cultivation Base for Nonmetal Composite and Functional Materials,Southwest University of Science and Technology,Mianyang 621010,PR China b

National Key Laboratory for Surface Physics &Chemistry,Mianyang 621907,PR China

a r t i c l e i n f o Article history:

Received 23April 2014

Received in revised form 12May 2014Accepted 16May 2014

Available online 28May 2014Keywords:

Iron borophosphate glass–ceramic Zirconium oxide Crystallization FTIR spectra

a b s t r a c t

The crystallization and structure of ZrO 2-doped 36Fe 2O 3–10B 2O 3–54P 2O 5glasses and crystalline com-pounds are studied by using X-ray diffraction and FTIR spectroscopy,respectively.It is found that the main crystallization is Fe 4(PO 4)2O,Fe 2(PO 4)O when 36Fe 2O 3–10B 2O 3–54P 2O 5glass with less than 6mol%of ZrO 2is heated at 850°C.When the doped ZrO 2is larger than 6mol%(including 6mol%),ZrP 2O 7crystallization appear.Furthermore,their crystallization behaviors suggest that ZrO 2can promote ZrP 2O 7crystallized from the ZrO 2-doped 36Fe 2O 3–10B 2O 3–54P 2O 5glass and restrain Fe 4(PO 4)2O and

Fe 2(PO 4)O crystallization formed due to the PO 3àgroups and PO 43à

phosphate groups gradually transform-ing into pyrophosphate P 2O 7

4àgroups with increasing content of ZrO 2.The knowledge provides an improved understanding of the role of Zr in the structure of iron borophosphate glasses and its crystalline compounds.

1.Introduction

Vitri?cation of high-level radioactive wastes (HLW),coming from reprocessing of spent nuclear fuel and nuclear industry,has been one of the most important methods to deal with for over half centuries [1–3]and is still a continual growing interesting by many researchers [2–6].Iron phosphate glasses have received consider-able attention in the past decades for their low melting tempera-ture,high chemical durability and good compositional ?exibility,aiming at utilizing them as host for certain toxic and nuclear wastes immobilization,especially to immobilize problematic radioactive wastes such as HLW containing high phosphates,sulfates,chlorides and some heavy metals [2,7–9].

However,thermal properties and irradiation stability of iron phosphate system glasses is lower than that of borosilicate glasses which have been chosen as HLW host material in industrial scale.According to the literature [10],B element has $2orders of magni-tude greater than those of P in thermal neutron absorption and mass absorption coef?cients,a fact prove to be useful in radioac-tive wastes immobilization.The literatures [11,12]have been shown that addition of boric oxide,B 2O 3,to some system glasses could improve their thermal stability and crystallization resistance,and B 2O 3also improves chemical durability in some phosphate glass systems [13].Further,the simultaneous presence of two glass formers (P 2O 5and B 2O 3)is expected to improve the conduction characteristics of some phosphate glasses [5].These effects of B 2O 3on properties of iron phosphate glasses are all desir-able for HLW immobilization.Thus,studies on boron contained iron phosphate glasses received suf?cient attention [14–20].The studied results of Fe 2O 3–B 2O 3–P 2O 5system glasses by Bingham et al.[15,16]and Karabulut [17]revealed that directly addition 10mol%of B 2O 3into 60P 2O 5–40Fe 2O 3glasses can give superior irradiation stability,thermal stability and has insigni?cant effect on its chemical durability comparing with the basic glass.The per-formances of 10mol%B 2O 3-doped 60P 2O 5–40Fe 2O 3glasses (36Fe 2O 3–10B 2O 3–54P 2O 5glasses)after immobilizing some other metal oxides were studied by our group [6,18,19],and the results showed that the good chemical durability and thermal properties of this system glasses still exist after adding 20mol%of Na 2O/K 2O,although some mixed alkali effect may exist [6],or 10–15mol%CeO 2which is often used as simulated element for nuclide Pu [18].However,this glass system has to be received comprehen-sive and fundamental investigation before utilizing as host glass for HLW immobilization in industrial scale.

Zirconium is a key constituent element of HLW glasses,occur-ring both as a ?ssion product and a fuel cladding component [20].The presence of large quantities of ZrO 2in certain high-level nuclear waste streams presents a signi?cant problem due to the relatively low solubility of ZrO 2in oxide glasses [20,21]and its

https://www.wendangku.net/doc/3810391766.html,/10.1016/j.jallcom.2014.05.117

?Corresponding author.Tel.:+86139********;fax:+8608162419202.

E-mail address:liaoqilong@https://www.wendangku.net/doc/3810391766.html, (Q.Liao).

strong ability to leads to the crystallization of glasses.Thus, vitri?cation of such a waste stream has great problems within the constraints of the current process due to limits of processing temperature(requiring temperature<1150°C)and the low solubil-ity of ZrO2in glass[20].As part of a wider research program have aimed at optimizing the solubility of zirconium in HLW glass wasteforms[21,22].

Therefore,to achieve the ef?cient immobilization of such nuclear waste streams,an understanding of the crystallization role of Zr within Fe2O3–B2O3–P2O5system glasses is required.In this study,the effect of different content of ZrO2(0mol%,3mol%, 6mol%,9mol%,12mol%and18mol%)on the crystallization of 36Fe2O3–10B2O3–54P2O5glass(IBP glass)is studied.The structure of crystallized ZrO2-doped36Fe2O3–10B2O3–54P2O5glass–ceramics is also investigated through FTIR analysis in detail.

2.Experimental

Raw materials that could produce50g of glass/ceramic products were prepared by mixing analysis grade Fe2O3,(NH4)H2PO4,H3BO3and ZrO2dry crystalline pow-ders according to the designed stoichiometric ratios in Table1.The thorough mixed raw materials were melted in a high temperature furnace at1200°C for about3h in air.After that,the melted products were quickly cooled to850°C,and maintain the temperature of850°C for3h to crystallize the products.Then,the temperature decreased to450°C at the rate of3°C minà1,these as-cooled crystallized products were annealed at450°C for1h to eliminate the stress of uncrystallized glasses and slowly cooled in furnace to room temperature for450min.Pure uncrystallized IBP glass was prepared by melting the batch at1200°C for3h in air.After stirring,the melted liquid was poured onto a preheated stainless steel plate.Then,the as-quenched glass was annealed at450°C for1h and slowly cooled to room temper-ature for450min.The as-prepared samples are marked by ZrO2content,for instance,Zr6sample represents36Fe2O3–10B2O3–54P2O5glass/ceramic containing 6mol%ZrO2.

The X-ray diffraction(XRD)patterns were obtained on a X’Pert PRO diffractom-eter(PANalytical Company(formerly Philips Analytical),Holland),using Cu K a radi-ation,in angular range of2h=3–80°.The collected XRD data were analyzed by using Jade6.5Software,the crystal structure of crystallized ceramics were obtained using Diamond3.2Software for assistance of analysis.The XRD of pure uncrystal-lized IBP glass was tested in angular range of2h=10–70°,also using Cu K a radiation.

To determine the temperature of crystallization and glass annealing,The glass transition temperature(T g),onset temperature of glass crystallization(T r)of pure uncrystallized IBP glass was obtained by DTA,at a heating rate of10°C minà1,using Thermal Analyzing Apparatus(Mettler Toledo,TGA/SDTA851e,Switzerland).The DTA measurements were performed in the temperature range100–1100°C in an air?ux and about sample weight of20mg was used for all measurements.A scan-ning electron microscope(Hitachi S-4800)was used to examine the morphologies of the glass–ceramics samples.Samples’structure was characterized by a Spectrum One Infrared Spectrometer(PerkinElmer Instrument https://www.wendangku.net/doc/3810391766.html,A).The FTIR spectra of the samples were measured from400to2000cmà1(wave number)at room tem-perature by standard KBr pellet method.Sample pellets were prepared by mixing and grinding a small quantity of glass powder with spectroscopic grade anhydrous KBr and then compressing the mixtures to form thin pellets for testing.

3.Results and discussion

The XRD pattern of the pure uncrystallized IBP glass is shown in Fig.1(a).It shows that the as-cast and annealed IBP glass is found to be amorphous.The DTA curve for the glass sample was obtained to determine the glass transition temperature(T g)and the crystallization onset temperature(T r)of the prepared IBP glass (Fig.1(b)).It is observed that the DTA curve is characterized with an endothermic peak,representing the glass transition phenome-non,with onset temperature of523°C,which corresponds to T g. T g is characteristic of structural relaxations taking place in the glass network and hence strongly depends on the nature of the struc-tural units constituting the glass network and their connectivity way[23].The DTA curve also shows the largest exothermic peak at about900°C,the onset temperature of which corresponds to crystallization onset temperature(T r=850°C).Thus,with the con-sideration of temperature increasing rate of the DTA testing,the crystallization temperature is determined to be850°C.In addition, the523°C of T g and327°C of T ràT g values for the IBP glass shows its high glass network stability and good thermal stability[6,23].

Fig.2(left)shows the XRD pattern of crystallized ZrO2-doped IBP glass and Fig.2(right)is its amplifying pattern in2h between 18°and29°to distinctly?nd their difference.As shown in Fig.2, the Zr0and Zr3glass–ceramic sample contain main crystallized products of Fe4(PO4)2O(JCPDS-PDF No.74-1443,space group: P21/c)and Fe2(PO4)O(JCPDS-PDF No.85-2386,space group:I41/ amd Z),FePO4(JCPDS-PDF No.84-0876,space group:P3121)crys-tallized products in trace,and no crystallization about compound containing Zr obtained,demonstrating that less than6mol%Zr can be?rmly immobilized in the36Fe2O3–10B2O3–54P2O5glass, even suffer crystallization.When the content of Zr is more than 6mol%,zirconium pyrophosphate ZrP2O7crystalline(JCPDS-PDF No.71-2286,space group:Pa-3)appeared.For Zr6and Zr9sample, the main crystallized products also are Fe4(PO4)2O and Fe2(PO4)O crystalline,just contain limited ZrP2O7and trace FePO4.For Zr12 sample,the main crystalline becomes ZrP2O7,just contain limited Fe4(PO4)2O and Fe2(PO4)O,and FePO4in trace.When the Zr content is up to18mol%(Zr18sample),the dominated crystalline is only ZrP2O7besides with limited FePO4,and the quantity of crystallized products Fe4(PO4)2O and Fe2(PO4)O is very trace.There are no crys-tallization about compound containing B element because B2O3is a stronger glass former oxide than P2O5,the B A O bond energy (498kJ/mol for[BO3])is much more than that of P A O(465–389kJ/mol).The crystallized products and its approximate content, according to Fig.2,of all samples are listed in Table2.

It can be concluded from Table2that the increasing content of ZrO2promote the ZrP2O7and FePO4crystallized from the ZrO2-doped36Fe2O3–10B2O3–54P2O5glass and restrain the Fe4(PO4)2O and Fe2(PO4)O crystallization formed when the glasses suffer crys-tallization.The crystallization behaviors suggest that the amount of the crystal FePO4and ZrP2O7increase with increasing the con-tent of ZrO2.It had been af?rmed that there are some structural similarities between iron phosphate glass and its crystallized crys-talline in terms of the iron coordination number(CN),iron valence and bonding of the phosphate groups[24].Therefore,the role of ZrO2in36Fe2O3–10B2O3–54P2O5glass can be deduced from the crystal structure of its crystallized products.Fig.3shows the ideal crystal structure,drawn by using Diamond3.2Software through their.cif?les,of the four crystallized product.The valence of iron in FePO4is3+(CN Fe=4),the average valence of iron in Fe4(PO4)2O is2+(CN Fe=4)and that of iron in Fe2(PO4)O crystallization is 2.5+(CN Fe=4or6).The valence and CN of Zr in ZrP2O7crystalliza-tion is4+and6,respectively.With the content of doped ZrO2 increase,the crystallization behavior discloses that the glass struc-ture become closer to the structure of crystalline of FePO4and ZrP2-O7,and Fe3+iron ions become higher concentration.The overall structural ordering of36Fe2O3–10B2O3–54P2O5glass becomes bet-ter with the content of the doped ZrO2increase,because Fe4(PO4)2-O and Fe2(PO4)O crystallization has much more disordering array of[PO4]tetrahedron than that of FePO4and ZrP2O7crystallization (Fig.3).The fundamental mechanism of structural ordering variation attribute the very strong cation?eld strength,Z/r2(Z is

Table1

Molar composition of glass–ceramics samples.

Samples Compositions(mol%)

Fe2O3B2O3P2O5ZrO2

Zr03610540

Zr334.929.752.383

Zr633.849.450.766

Zr932.769.149.149

Zr1231.688.847.5212

Zr1829.528.244.2818

F.Wang et al./Journal of Alloys and Compounds611(2014)278–283279

element valence,r ionic radius),of Zr4+which has strong ability to orderly arrange the surrounding atoms or ions according to its own required coordination numbers[25].

The SEM images of the crystallized ZrO2-doped IBP glass sam-ples are shown in Fig.4.It can be seen from the?gure that the compactability of the crystallized ZrO2-doped IBP glass samples become better when the content of ZrO2is less than6mol%,and that of glass–ceramic samples begin to become worse with contin-ual increasing content of doped-ZrO2from6mol%to18mol%.The compactability of the IBP glass becomes better when appropriate ZrO2doped into the IBP base glass for the higher cation?eld strength,Z/r2,of Zr4+(7.716)than that of Fe2+(5.375),therefore, the compactability of the crystallized ZrO2-doped IBP glass sam-ples becomes better.For6mol%ZrO2-doped sample(Zr6),the best compactability obtained for ZrP2O7crystallization appeared in trace.However,continual increasing content of doped-ZrO2,large amount of ZrP2O7,which has dense crystal structure,crystallized from the ZrO2-doped IBP glass,some big pores appeared in the crystallized product.When12mol%of ZrO2doped in the IBP glass, big pores disappeared and uniform?ne crystallized products obtained(Fig.4(e))because the content of ZrP2O7crystallization

Fig.1.(a)XRD pattern and(b)DTA curve of the prepared IBP glass.

Fig.2.XRD pattern of the crystallized ZrO2-doped IBP glasses.

Table2

The crystallized products of samples and its approximate content.

ZrO2content

(mol%)

Crystallized products(approximate content)

0FePO4(trace),Fe4(PO4)2O(main),Fe2(PO4)O(main)

3FePO4(trace),Fe4(PO4)2O(main),Fe2(PO4)O(main)

6ZrP2O7(trace),FePO4(trace),Fe4(PO4)2O(main),Fe2(PO4)O

(main)

9ZrP2O7(limit),FePO4(trace),Fe4(PO4)2O(main),Fe2(PO4)O

(main)

12ZrP2O7(main),FePO4(trace),Fe4(PO4)2O(limit),Fe2(PO4)O

(limit)

18ZrP2O7(main),FePO4(limit),Fe4(PO4)2O(very trace),

Fe2(PO4)O(very trace)

increase and the crystallized Fe4(PO4)2O and Fe2(PO4)O decrease. For18mol%ZrO2-doped sample(Zr18),the main crystallized crys-tallization is ZrP2O7,and the content of crystallized FePO4is lim-ited,and the quantity of crystallized products Fe4(PO4)2O and Fe2(PO4)O which has less structural ordering than that of ZrP2O7 and FePO4is very trace,thus,the crystallized products are porosity and loose compactability for large volume changes happened

the prepared ZrO2-doped IBP glass–ceram-

2000cmà1are shown in Fig.5.FTIR spectrum information about molecular vibration or rotation molecular bonds,and is usually used to investigate

in composition.In general,there are no sig-

between the infrared spectra of the studied

no additional peak appeared and old peak

the peak positions of some bands appears

different content of doped ZrO2(related to

numbers of bridging and nonbridging oxygens

strength of Zr4+).It is known that the spectral broadening is consistent with the samples’structure accommodat-ing many types of bonding state or the overlap of vibration absor-bance for two or more bonding state.In order to get quantitative information about speci?c structure,the FTIR spectra are deconvo-luted using a Gaussian-type function[6,26].Fig.6shows the spe-ci?c deconvolution spectrum for some prepared ZrO2-doped IBP glass–ceramics.It is expected that the observed IR vibration modes mainly represent the structural network

besides the sharing of some tetrahedral

([BO4],[BO3])unit groups[27].Take this

combine the literature data,the experimental

interpreted as follows:

The band between416and488cmà1corresponds

of bending vibration of O@P A O linkages,[ZrO

[28–30],and the band around444–519cm

monics of P A O A P bending vibrations in phosphate

The absorption band between519and592

assigned to the bending mode of O A P A O in

[31].The absorption band at584–597cmà

Fig.3.Ideal crystal structure of(a)FePO4,(b)Fe4(PO4)2O,(c)Fe2(PO4)O and(d)ZrP2O7containing[PO4]tetrahedron.

Fig.4.SEM images of the(a)Zr0,(b)Zr3,(c)Zr6,(d)Zr9,(e)Zr12and(f)Zr18glass–ceramic samples.

bending(or)lattice mode vibrations,speci?cally also related to pyrophosphate P2O7groups[32].The band around630–639cmàcorresponds to the stretching vibrations of Fe A O A P bonds[33] The band at713–767cmà1may be due to bending vibrations of A O A B bonds in borate networks([BO4]group)[34],indicating that groups consists of two boron–oxygen units by sharing oxygen probably exist in borophosphate glass systems.The band at790–903cmà1could be assigned to symmetric modes of P A O A P bonds in(P2O7)4àanions[35].In addition,when B exist in the structure of phosphate glass,the formation of P A O A B linkages is suggested by broadening band about790–903cmà1(which is due exclusively to the B A O stretching of the[BO4]units)[36].Therefore,Groups consists of[PO4]and[BO4]units to form[BP]O4by sharing the neg-ative charge supplied by the oxygen of the modi?er also probably exist in the glass–ceramics[37].The band at about890–974cmàis characteristic of the stretching vibrations of B A O bonds in[BO4 units[38].The band due to the asymmetric stretching vibrations of PO43àgroups(Q0group)is located between957and1041cmà[39,31].Meanwhile,the band between1084and1106cmà1 attributed to the symmetric stretching vibrations of PO43àtetrahe-dra(POàionic group)[6,31].The characteristic band of1114–1244cmà1can be considered as the PO3àgroups(Q2group)[31]

à1

dences of the relative areas of the groups corresponding to the

main structural groups on ZrO2content for the studied glass–cera-mic samples.It is known that the dimension of relative area for one group or bond is proportional to the quantity of the corresponding group or bond in FTIR spectra[6,32,35].Doping less than6mol%of ZrO2into the36Fe2O3–10B2O3–54P2O5glass,the crystallized crys-tallizations are about same,at the same time,ZrO2brings in free oxygen into the glass structure,which lead to[BO3]group trans-forming to[BO4]group in samples.However,with continual increasing the content of doped ZrO2,crystallization ZrP2O7appear,[BO4]group begin to change into[BO3]group,especially the crys-tallized ZrP2O7appeared in large content(Zr18sample),the quan-tity of[BO3]group is much more than that of[BO4]group.With the increasing content of ZrO2,the amount of crystallized zirconium pyrophosphate ZrP2O7change from zero,trace,limit to main, which may demonstrate that the existence of Zr in structure facil-itate the formation of pyrophosphate P2O74àgroups.Therefore, other phosphate groups such as PO3àgroups and PO43àgroups change into pyrophosphate P2O74àgroups in the in?uence of strong

Fig.5.FTIR spectra for the prepared ZrO2-doped IBP glass–ceramics.

Fig.6.Deconvolution spectrum for(a)Zr0,(b)Zr6and(c)Zr12glass–ceramic

samples.

cation ?eld strength of Zr 4+,the amount of PO 3àgroups and PO 43à

groups decrease (Fig.7).

Iron phosphate glasses with compositions around the pyro-phosphate stoichiometry have been proposed by others [24,42,43],That is,Q 1-tetrahedra dominate the phosphate anions that constitute the structures of these glasses,with Q 0-and Q 2-tet-rahedra also present.The relative concentrations of the three tetra-hedron may change rely on the following disproportionation reaction [43,44]:

2Q 1$Q 2tQ 0

e1T

The FTIR spectra from more complex iron phosphate glasses,for example,those containing other oxides,can be interpreted in a similar manner.Thus,the above-mentioned transformations of

PO 3à(Q 2),P 2O 74à(Q 1)and PO 43à

(Q 0)groups may accord to the reac-tion Eq.(1),and Fe 4(PO 4)2O and Fe 2(PO 4)O crystallization products are depressed greatly.4.Conclusions

The crystallization of ZrO 2-doped 36Fe 2O 3–10B 2O 3–54P 2O 5glasses and the structure of its crystallized glass–ceramics have been investigated in detail.The main products of Fe 4(PO 4)2O,Fe 2(PO 4)O crystallized from the studied glass with less than 6mol%ZrO 2is heated at 850°C.More than 6mol%(including 6mol%)ZrO 2doped into the glass,ZrP 2O 7crystallization appear.

Moreover,PO 3àand PO 43à

phosphate groups change into pyrophos-phate P 2O 74àgroups with increasing Zr content for the strong cation ?eld strength of Zr element.Moreover,The increasing content of ZrO 2promote the ZrP 2O 7crystallized from the ZrO 2-doped IBP glass and restrain the Fe 4(PO 4)2O and Fe 2(PO 4)O crystallization formed.The obtained conclusions can offer some useful informa-tion for the study and application of immobilization and disposal of HLW containing Zr.Acknowledgements

The funds supported by Southwest University of Science and Technology (11zx2101and 13zx7130),the National Basic Research

Program of China (973Program No.2012CB722707)and the National Natural Science Foundation of China (91126015)are greatly acknowledged and appreciated.References

[1]C.L.Crawford,J.C.Marra,N.E.Bibler,J.Alloys Comp.444(2007)569–579.[2]G.K.Marasinghe,M.Karabulut,C.S.Ray,D.E.Day,D.K.Shuh,P.G.Allen,M.L.

Saboungi,M.Grimsditch,D.Haeffner,J.Non-Cryst.Solids 263(2000)146–154.[3]R.K.Mishra,P.U.Sastry,A.K.Tyagi,C.P.Kaushik,K.Raj,J.Alloys Comp.466

(2008)543–545.

[4]P.Loiseau,D.Caurant,P.Hrma,J.Nucl.Mater.402(2010)38–54.

[5]N.Sdiri,H.Elhouichet,B.Azeza,F.Mokhtar,J.Non-Cryst.Solids 371(2013)22–

27.

[6]F.Wang,Q.L.Liao,G.H.Xiang,S.Q.Pan,J.Mol.Struct.1060(2014)176–181.[7]W.H.Huang,D.E.Day,C.S.Ray,C.W.Kim,J.Nucl.Mater.346(2005)298–305.[8]D.E.Day,Z.Wu,C.S.Ray,J.Non-Cryst.Solids 241(1998)1–12.

[9]S.K.Fong,I.W.Donald,B.L.Metcalfe,J.Alloys Comp.444(2007)424–428.[10]P.A.Bingham,G.Yang,R.J.Hand,G.M?bus,Solid State Sci.10(2008)1194–

1199.

[11]I.W.Donald,B.L.Metcalfe,J.Non-Cryst.Solids 348(2004)118–122.

[12]T.Harada,H.Takebe,M.Kuwabara,J.Am.Ceram.Soc.89(2005)247–250.[13]L.Koudelka,P.Mo?ner,J.Non-Cryst.Solids 293–295(2001)635–641.

[14]A.Mogu?-Milankovic

′,L.Pavic ′,H.Ertap,M.Karabulut,J.Am.Ceram.Soc.95(2012)2007–2014.

[15]P.A.Bingham,R.J.Hand,S.D.Forder,https://www.wendangku.net/doc/3810391766.html,vaysierre,F.Deloffre,S.H.Kilcoyne,I.

Yasin,Phys.Chem.Glasses-B 47(2006)313–317.

[16]P.A.Bingham,R.J.Hand,S.D.Forder,Mater.Res.Bull.41(2006)1622–1630.[17]M.Karabulut,B.Yuce,O.Bozdogan,H.Ertap,G.M.Mammadov,J.Non-Cryst.

Solids 357(2011)1455–1462.

[18]Q.L.Liao,F.Wang,S.Q.Pan,H.Liao,Chin.J.Nucl.Radiochem.32(2010)336–

341.

[19]H.M.Qin,Q.L.Liao,S.Q.Pan,W.Wang,Chin.Atom.Energy Sci.Technol.15

(2011)1421–1426.

[20]A.J.Connelly,N.C.Hyatt,K.P.Travis,R.J.Hand,E.R.Maddrell,R.J.Short,J.Non-Cryst.Solids 357(2011)1647–1656.

[21]A.J.Connelly,K.P.Travis,R.J.Hand,N.C.Hyatt,E.Maddrell,J.Am.Ceram.Soc.

94(2011)137–144.

[22]F.Angeli,T.Charpentier,M.Gailard,P.Jollivet,J.Non-Cryst.Solids 354(2008)

3712–3722.

[23]A.Hruby

′,Czech J.Phys.22(1972)1187–1193.[24]X.Y.Fang,C.S.Ray,A.Mogu?-Milankovic

′,D.E.Day,J.Non-Crys.Solids 283(2001)162–172.

[25]L.M.Zhang,X.H.Huang,X.L.Song,Fundamentals of Materials Science,Wuhan

University of Technology Press,2008.

[26]D.A.Magdas,O.Cozar,V.Chis,I.Ardelean,Vib.Spectrosc.48(2008)251–254.[27]A.M.Abdelghany, F.H.ElBatal,M.A.Azooz,M.A.Ouisb,H.A.ElBatalb,

Spectrochim.Acta,Part A 98(2012)148–155.

[28]P.Pascuta,G.Borodi,N.Jumate,J.Alloys Comp.504(2010)479–483.

[29]B.X.Liu,X.J.Lin,L.Y.Zhu,X.Q.Wang, D.Xu,Ceram.Int.(2014),http://

https://www.wendangku.net/doc/3810391766.html,/10.1016/j.ceramint.2014.03.025.

[30]C.Dayanand,G.Bhikshamaiah,V.J.Tyagaraju,M.Salagram,J.Mater.Sci.31

(1996)1945–1967.

[31]D.A.Magdas,O.Cozar,V.Chis,I.Ardelean,N.Vedeanu,Vib.Spectrosc.48

(2008)251–254.

[32]A.M.Abdelghany,M.A.Ouis,M.A.Azooz,H.A.EllBatal,Spectrochim.Acta,Part

A 114(2013)569–574.

[33]K.Joseph,https://www.wendangku.net/doc/3810391766.html,indan,P.Chandramohan,R.P.R.Vasudeva,J.Nucl.Mater.

384(2009)262–267.

[34]M.Abid,M.Et-Sabiron,M.Taibi,J.Mater.Sci.Eng.B 97(2003)20–26.

[35]S.Rani,S.Sanghi,A.Agarwal,V.P.Seth,Spectrochim.Acta,Part A 74(2009)

673–677.

[36]S.Agathopoulos,D.U.Tulyaganov,J.M.G.Ventura,S.Kannan,A.Saranti,M.A.

Karakassides,J.M.F.Ferriera,J.Non-Cryst.Solids 352(2006)322–328.[37]L.Koudelka,P.Mo?ner,Mater.Lett.42(2000)194–199.

[38]S.P.Singh,R.P.S.Chakradhar,J.L.Rao,B.Karmakar,J.Alloys Comp.493(2010)

256–262.

[39]P.Subbalakshmi,N.Veeriah,J.Non-Cryst.Solids 298(2002)89–98.[40]S.Kabi,A.Ghosh,J.Phys.Chem.C 115(2011)9760–9766.

[41]F.H.ElBatal,S.Ibrahim,A.M.Abdelghany,J.Mol.Struct.1030(2012)107–112.[42]A.Mogus-Milankovic, B.Pivac,K.Furic,D.E.Day,Phys.Chem.Glasses 38

(1997)74–78.

[43]L.Y.Zhang,K.B.Richard,J.Am.Ceram.Soc.94(2011)3123–3130.

[44]J.R.Van Wazer,Phosphorus and its Compounds,Interscience,New York,NY,

1958

Fig.7.Relative areas dependence of groups related to the vibrational modes of main network groups versus ZrO 2content.The lines are drawn as a guide for the eye.

Compounds 611(2014)278–283283