Synthesis and Characterization of W–Cu Nanopowders by a Wet-chemical Method-2011

8112019 Synthesis and Characterization of WndashCu Nanopowders by a Wet-chemical Method-2011

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Synthesis and characterization of WndashCu nanopowders by a wet-chemical method

Lei Wan Jigui Cheng Peng Song Yonghong Wang Tao Zhu

School of Materials Science and Engineering Hefei University of technology Hefei 230009 PR China

a b s t r a c ta r t i c l e i n f o

Article history

Received 26 August 2010

Accepted 19 January 2011

Available online xxxx

Keywords

WndashCu nanopowder

Wet-chemical method

Precursors

Ratio of W to Cu

Hydrogen reduction

A wet-chemical process was employed to prepare WndashCu nanopowders Precursors containing some

tungstates were obtained by adding precipitants into a complex solution containing ammonium

metatungstate and copper nitrate afterwards spray-drying the complex solutions The precursor powders

were then calcined and hydrogen-reduced to convert into Wndash

Cu powders Phase constitution andmorphology of the precursors the calcined powders as well as the reduced powders were characterized

Relations between the ratio of W to Cu in the complex solutions and the phase constitution of the calcined

precursors were investigated The effects of the reduction temperature and H 2 1047298ow rate on the hydrogen

reduction kinetics and the crystallite size of the WndashCu powder were also studied It was shown that the wet-

chemical process produces WndashCu powders with nanosized particles of about 100 nm The composition of the

calcined precursors varieswith theratioof W to Cu in thecomplexsolution andonly CuWO4 was found inthe

calcined precursors when the ratio of W to Cu is 7426(wt) The reduction temperature and H 2 1047298ow rate

have a great in1047298uence on the hydrogen-reduction process and the crystallite size of the resulting W ndashCu

powders

copy 2011 Elsevier Ltd All rights reserved

1 Introduction

WndashCu alloys combine advantages of W-phase having high

strength and low thermal expansion coef 1047297cient with Cu-phase having

high thermal and electrical conductivity They have been widely used

for heavy-duty electrical contacts arcing resistance electrodes heat

sink materials and many other applications [1ndash3] In most of the

applications high-dense WndashCu materials with homogeneous micro-

structure are required for high performance WndashCu materials are

commonly fabricated by copper in1047297ltration sintering or by liquid

phase sintering of WndashCu powder compacts [4] However because of

themutual insolubility and thelow wettabilty between W and Cu it is

dif 1047297cult to sinter WndashCu materials to full density by liquid phase

sintering Furthermore the application of copper in1047297ltration tech-

nique is also limited because it is dif 1047297cult to accurately control the Cu

content in theparts and it mayintroduce defects in the structure [56]

Although a small amount of activatorssuch as Ni Co Fe etc enhance

signi1047297cantly the sinterability of the WndashCu system such activators also

have some negative effects on the thermal and electrical conductivity

of the WndashCu materials [7] Therefore attempts have been made to

improve the sinterability of the WndashCu powder compacts It is well-

known that using nano-sized and well-dispersed powders can

effectively improve sinterability of a powder compact especially in

a liquid phase sintering system such as WndashCu material in which the

dominant sintering mechanism is known to be a particle rearrange-

ment [89] Accordingly many methods have been explored toprepare ultra-1047297ne or even nanosized WndashCu powders to improve

their sinterability [10] It has been reported that WndashCu nanopowders

can be fabricated by purely mechanical methods such as mechanical

alloying (MA) [11] It has also been shown that super1047297ne WndashCu

powders can be prepared by mechano-chemical process from mixes

of tungsten and copper oxides [12] However the mechanical-milling

process is liable to introduce impurity into the powders which

decreases physical property of the resulting WndashCu materials [13]

Recently some wet-chemical methods such as co-precipitation

solndashgelspray-drying and other processes have been tried to synthe-

size WndashCu nanopowders with high purity and excellent sinterability

[14ndash17] In the wet-chemical processes some soluble tungstates were

used as raw materials to synthesize precursors which were then

converted into WndashCu powder by calcinations and reduction Mean-

while the conventional mechanical-milling was replaced by wet-

mixing to improve homogeneity of the reactants However a series of

compound salts mayform in an aqueous solution containing tungstate

and copper ions and the composition of the precursors as well as the

resultant WndashCu powders may depend greatly on the stoichiometric

amount (eg ratio of tungsten to copper) in thesolution Furthermore

the H2 1047298ow rate and reduction temperature also have a great effect on

the reaction rate of the hydrogen-reduction process and the particle

size of the resultant WndashCu powders [1819]

In this work a simple and convenient wet-chemical process was

designed to synthesize WndashCu composite powders The dependence of

composition of the precursorson the ratio of W to Cu was studied and

Int Journal of Refractory Metals and Hard Materials xxx (2011) xxx ndashxxx

Corresponding author Fax +86 551 2901793

E-mail address jgcheng63sinacom (J Cheng)

RMHM-03210 No of Pages 6

0263-4368$ ndash see front matter copy 2011 Elsevier Ltd All rights reserved

doi101016jijrmhm201101006

Contents lists available at ScienceDirect

Int Journal of Refractory Metals and Hard Materials

j o u r n a l h o m e p a g e w w w e l s ev i e r c o m l o c a t e I J R M H M

Please cite this article as Wan L et al Synthesis and characterization of WndashCu nanopowders by a wet-chemical method Int J Refract MetHard Mater (2011) doi101016jijrmhm201101006



the effects of the reduction temperature and H2 1047298ow rate on the

hydrogen reductionrate andcrystallite size of theWndashCu powderwerealso investigated The present work has shown that the wet-chemical

process can produce well-dispersed WndashCu powders with mean

particle size of about 100 nm

2 Experimental

21 Preparation of W ndashCu powders

Ammonium metatungstate and copper nitrate solutions were 1047297rst

prepared by dissolving corresponding salts in distilled water The

solutions were then mixed according to different stoichiometric ratios

of W toCu(Wndash20 wtCu Wndash26 wtCu andWndash30 wtCu) Complex

solutions were obtained by adding aqueous ammonia precipitant into

the mixed solutions and maintaining the pH value at about 6Precursor powders were obtained by spray-drying the complex

solution at a temperature of about 200 degC The precursor powders

were subsequently calcined at 600 degC followed by reducing in H2 at

800 degC for 1 h to convert into WndashCu powders The height of the

calcined powder bed is about 10 mm dew point and 1047298ow rate of H2

are negative 50 degC and 100 mlmin respectively

22 Characterization

Simultaneous differential thermal analysis and thermogravimetry

(DTA-TG) were carried out on the dried precursor powders The

samples were heated from room temperature to 800 degC at a heating

rate of 10 degCmin under a dynamic air 1047298ow The precursors and the

calcined powders with different ratios of W to Cu as well as the

resulting WndashCu powders were characterized by X-ray diffractometer

(XRD) Grain size of W and Cu in the WndashCu powders reduced atdifferent temperature was calculated according to the Scherrer

equation Particle size and morphology of the precursor powders

the calcined powders and the resulting WndashCu powders were

examined by transmission electron microscope (TEM) and scanning

electron microscope (SEM) Weight loss of the calcined precursors

under different reduction temperatures and H2 1047298ow rate was

measured using a thermal balance to analyze the kinetics of the

reduction process

Fig 1 XRD patterns of the dried precursors with different ratios of tungsten to copper a) W-26 wtCu b) W-20 wtCu c) W-30 wtCu

Fig 2 DTA-TG results of the Wndash

26 wtCu precursors

2 L Wan et al Int Journal of Refractory Metals and Hard Materials xxx (2011) xxxndash xxx




3 Results and discussion

31 Characterization of the precursor powders

Fig 1(a) shows the XRD patterns of dried precursor powders with

different ratiosof W toCu Whenthemass ratio ofW to Cuis 7426there

exist Cu(NH3)2NO3 Cu2WO4(OH)2 and (NH3)4H2W12O40middotxH2O in the

precursors Fig 2 shows DTA-TG curves of the Wndash26 wtCu precursor

powders obtained in air at a heat rate of 10 degCmin A mass loss of about

2 below 80 degC is accompanied by an endothermic peak at about 80 degC

which indicates the removal of remanet water in the precursors Another

mass loss of about 5 at 90 degCndash250 degC can be ascribed to the removal of

crystal water andthe formationof Cu2WO4(OH)2 and(NH4)2WO4middotxH2O

This is corresponded to the two endothermic peaks at 130 degC and 180 degC

In a temperature range of 250 degCndash

300 degC there occurs an apparentexothermic peak in the DTA curves with a mass loss of about 40 which

may be caused by the complete decomposition of ammonium ion No

apparent mass loss occurs at a temperature above 300 degC indicating the

formation of oxides of copper and tungsten

Fig 3 shows SEM photographs of the spray-dried Wndash26 wtCu

precursor powders The powders have a particle size of about 100ndash

200 nm The ultra1047297ne particle size makes the particle prone to

aggregation and a shelf structure was observed in the precursor

powders

To further investigate the effects of the ratio of W to Cu in the

complex solution on the composition of the precursor powders The

precursors of containing Wndash20 wtCu and Wndash30 wtCu were also

preparedand characterized Fig 1(b)and (c)shows theXRD patterns

of dried precursor powders with different ratios of W to Cu (Wndash

20 wtCu and Wndash30 wtCu) There exist (NH3)4H2W12O40middotxH2O

(NH3)10H2W12O42middot4H2O (NH4)2WO4middotxH2O Cu2WO4 (OH) 2 in the

XRDpatterns of the Wndash20 wtCu precursor powders However only

Cu (NH3)2NO3 and Cu2WO4 (OH)2 are observed in the Wndash30 wtCu

precursor powders Comparing (b) and (c) with (a) it can deduce

that copper ions are easy to combine with the radical tungstate to

form composite salts in the precursors as copper ionic concentration

increases and the excessive copper ions can react with the residual

ammonium ions in the solution to form Cu(NH3)2NO3

32 Characterization of the calcined powders

Fig 4 shows the XRD patterns of the calcined Wndash26 wtCu

precursor powders It can be seen that CuWO4 is not completely

formed in the powders by calcining precursors at 500 degC Howeveronly CuWO4 was found in the powder calcined at 600 degC and 700 degC

and the degree of peak broadening decrease with the increasing

calcination temperature which indicates the growth of the crystallite

size of the resulting powders

Fig 5 shows the XRD patterns of the 600 degC calcined precursors

with different ratios of W to Cu (Wndash20 wtCu and Wndash30 wtCu)

There exist WO3 and CuWO4 in the calcined Wndash20Cu precursor

powders This indicates that there are excessive tungsten ions in the

Fig 3 SEM photographs of the dried Wndash26 wtCu precursors

Fig 4 XRD patterns of the Wndash26 wtCu precursor calcined at different temperatures

Fig 5 XRD patterns of the calcined precursors at 600 degC with different ratios of W to Cu a) W-20 wtCu b) W-30 wtCu

3L Wan et al Int Journal of Refractory Metals and Hard Materials xxx (2011) xxxndash xxx




solution to form CuWO4 In the context of 70 W30Cu CuO and

CuWO4 are observed in the calcined precursor powders indicating

that copper ions are excessive to tungstate ions to form CuWO4

Comparing Fig 5 with Fig 4 it is clear that the ratio of W to Cu in the

complex solution has an effect not only on the composition of the

spray-dried precursors but also on the calcined precursors

33 Characterization of the reduced powders

Fig 6 shows the XRD patterns of the Wndash26 wtCu composite

powders by reducing the calcined precursors at different tempera-

tures The composite powders are just composed of W and Cu phases

and no residual metallic oxides are found The intensity of the XRD

peaks increases with the reduction temperature which indicates the

growth of crystallite size of W and Cu in the WndashCu composite

powders According to the Scherrer Equation (Dhkl=kλ β cosθ k =089 β and θ is full width at half maximum intensity and diffraction

angle respectively) that grain size in the WndashCu powders is 2015 nm

2356 nm and 2878 nm for W at reduction temperatures of 800 degC

900 degC and 1000 degCrespectively and is 1952 nm 2291 nm and

2845 nm for Cu respectively

In the experimental the phase constitute of the reduced precursors

with the weight ratio of W to Cu of Wndash20 wtCu and Wndash30 wtCu

respectively wasalso detected by XRD Fig 7 shows the XRD patterns of

the precursors reduced in H2 at 800 degC for 1 h with different ratios of W

to CuAll the reduced precursors are just composed of W and Cu phases

Table 1 lists the grain size of W and Cu phases in the resultant WndashCu

powders with different ratios of W to Cu under different reduction

temperatures As the case of Wndash26 wtCu powders the grain size of

both W and Cu phases in the Wndash20 wtCu and Wndash30 wtCu powders

also increases as the reduction temperature increases It is also clearly

seen from Table 1 thatthe grain sizeof W decreases as the ratio of W to

Cu in the precursor decreases but the grain size of Cu shows a reverse

change Thiscan beascribedto that asthe ratio of W to Cudecreases the

Fig 6 XRD patterns of the Wndash26 wtCu powders by reducing the calcined powders at

different temperatures

Fig 7 XRD pattern of the Wndash

Cu powders reduction at 800 degC with different ratios of W to Cu





amount of Cu in the resultant powder increases which facilitates the

growth of the Cu grains and restrains the growth of the W grains

Fig 8 shows the TEM images of the Wndash26 wtCu powders by

reducing the calcined precursors at different temperatures The 800 degC

reduced powders show a granular shape and have a particle size of

about 100 nm with a narrow particle size distribution However the

mean particle size increasesto about 150and 200 nm as the reduction

temperature increases to 900 degC and 1000 degC respectively

34 Kinetics of the H 2-reduction

The effects of the reduction temperature and H2 1047298ow rate on the

reactionratio of the calcinedWndash26 wtCu precursors areshown in Fig9

The calcined precursors are completely converted into WndashCu powders at

800 degC in 60 min with an H2 1047298ow rate of 100 mlmin (Fig 9(a)) This

temperature is lower than that needed to reduce pure tungsten oxide by

H2 [18] This may be ascribed to that the copper oxide in the precursor is

easy to reduce into Cu at a low reduction temperature (300 degCndash400 degC)

and this Cu may act as a nucleation site of W which facilitates the

reduction of tungsten oxides However much longer time is needed to

achieve the same reduction ratio at the same H2 1047298ow rate when

the reduction temperature decreases to 600 degC and 700 degC respectively

Fig 9(b) shows the effects of H2 1047298

ow rate on the reduction ratio of thecalcined Wndash26 wtCu precursors When the H2 1047298ow rate is 100 mlmin

it needs 1 h to convert the precursors into WndashCu However the same

process takes much longer time when the H2 1047298ow rate lowers to 80 ml

min and 60 mlmin respectively This may be ascribed that a faster H2

1047298ow rate can take away the moisture generated in the reaction to speed

up the reduction process

Fig 10 shows the effects of the reduction temperature on the

reaction ratio of the calcined Wndash20 wtCu and the Wndash30 wtCu

precursors The precursors with a composition of Wndash20 wtCu and

Wndash30 wt were also reduced into WndashCu alloy powders Cu at 800 degC

in60 min withan H2 1047298ow rate of 100 mlmin which is consistent with

the case of Wndash26 wtCu By comparing Fig 10 with Fig 9(a)it can

also be seen that as W fraction in the precursors decreases the time

needed to achieve the same reduction ratio reduces This proves again

the promotion role of Cu for the reduction of the tungsten oxides

Table 1

Grain size of W and Cu with different ratios of W to Cu under different reduction

temperatures

Grain size of Wnm Grain size of Cunm

Reduction temperature 800 degC 900 degC 1000 degC 800 degC 800 degC 1000 degC

Wndash20 wtCu 2477 2763 3217 1833 2003 2372

Wndash26 wtCu 2015 2356 2878 1952 2291 2845

Wndash30 wtCu 1983 2205 2525 2213 2502 3210

Fig 8 TEM images of the Wndash26 wtCu powders reduced at different temperatures a) 800 degC b) 900 degC c) 1000 degC

Fig 9 Effect of the reduction temperature and H2 1047298ow rate on H2-reduction rate





To further investigate the kinetics of the H2-reduction process of

the precursors activation energy (Ea) of the H2-reduction process can

be calculated according to the Arrhenius equation

Kr = K0exp minusEa = R gT

where Kr is the velocity constant of the reduction reaction calculated

from Fig 9(a) K0 is the frequency factor R g is the gas constant and T is

the absolute temperature According to the data shown in Fig 9(a)

the velocity constant of reduction Wndash26 wtCu precursors is

02867min 01650min and 01480min at reduction tempera-

tures of 800 degC 700 degC and 600 degCrespectively Therefore the average

reduction activation energy from room temperature (RT) to 800 degC

canbe calculated from theslopes of lnKrminusTminus1 curves andthe value is

about 251 kJmol

4 Conclusions

WndashCu composite powders with different ratio of W to Cu were

successfully synthesized from ammonium metatungstate and copper

nitrate by a wet-chemical method The powders have a mean particle

size of about 100 nm with a narrow particle size distribution The

composition of the precursors changes with the stoichiometric ratio of

W and Cu in the complex solutions and only CuWO4 is found in the

74 W26Cu precursor samples The reduction temperature H2 1047298ow

rate and ratio of W to Cu have a great in1047298uence on the hydrogen-

reductionprocessThe reaction ratio increases with theincreaseof the

reduction temperature the H2 1047298ow rate and the composition of theprecursors The average reduction activation energy for Wndash26 wtCu

is about 251 kJmol at room temperature (RT) to 800 degC

Acknowledgements

This work was 1047297nancially supported by the Natural Science

Foundation of Education Bureau of Anhui Province of China under

contract no KJ2010A274

References

[1] Ardestani M Rezaie HR Arabi H Razavizadeh H The effect of sinteringtemperature on densi1047297cation of nanoscale dispersed Wndash20ndash40wt Cu compositepowders Int J Refract Met Hard Mater 200927862ndash7

[2] Ozer O Missiaen JM Lay S Mitteau R Processing of tungstencopper materialsfrom WndashCuO powder mixtures Mater Sci Eng A 2007460ndash1 525-31

[3] Kim DG Oh ST Jeon H Lee CH Kim YD Hydrogen-reduction behavior andmicrostructural characteristics of WO3ndashCuOpowdermixtureswith various millingtime J Alloy Comp 2003354239ndash42

[4] German RM Suri P Park SJ Review liquid phase sintering J Mater Sci 2009441ndash39

[5] Cheng J Lei C Xiong E Jiang Y Xia Y Preparation and characterization of WndashCunanopowders by a homogeneous precipitation process J Alloy Comp 2006421146ndash50

[6] Li Y Qu X Zheng Z Lei C Zou Z Yu S Properties of W ndashCu composite powderproduced by a thermo-mechanical method Int J Refract Met Hard Mater 200321259ndash64

[7] Kim GS Kim YD Oh ST The initial stage of sintering for the WndashCu nanocompositepowder prepared from WndashCuo mixture Mater Lett 200458578ndash81

[8] Kang HK Kang SB Tungstencopper composite deposits produced by a cold spray

Scr Mater 2003491169ndash74[9] Cheng J Song P Gong Y Cai Y Fabrication and characterization of Wndash15Cu

composite powders by a novel mechano-chemical process Mater Sci Eng A2008488453ndash7

[10] Fan J Zhu S Liu T Current research on fabrication of WndashCu nanocompositepowder Cemented Carbide 200825252ndash6

[11] Maneshian MH Simchi A Hesabi ZR Structural changes during synthesizing of nanostructured Wndash20 wt Cu composite powder by mechanical alloying MaterSci Eng A 200744586ndash93

[12] Kim DG Lee BH Oh ST Kim YD Kang SG Mechanochemical process for Wndash15 wtCu nanocomposite powders with WO3ndashCuO powder mixture and its sinteringcharacteristics Mater Sci Eng A 2005395333ndash7

[13] Ryu SS Kim YD Moon IH Dilatometric analysis on the sintering behavior of nanocrystalline WndashCu prepared by mechanical alloying J Alloy Comp 2002335233ndash40

[14] Liu T Fan J Cheng H Tian J Phase transformation of solndashspray dried WndashCuprecursor powder during calcining Chin J Nonferrous Met 2008182202ndash6

[15] Shi X Yang H Wang S Shao G Duan X Zhen X et al Characterization of Wndash20Cu

ultra1047297

ne composite powder prepared by spray drying and calciningndash

continuousreduction technology Mater Chem Phys 2007104235ndash9[16] Amirjan M Zangeneh-Madar K Parvin N Evaluation of microstructure and

contiguity of WCu composites prepared by coated tungsten powders Int J RefractMet Hard Mater 200927729ndash33

[17] Fan J Liu T TianJ Cheng H HuangB Phase transformation duringsynthesis of Wndash

50Cu nanocomposite powder by spray-drying and hydrogen reduction processRare Met Mater Eng 2008371919ndash23

[18] KimGS LeeYJ KimDG OhST Kim DS KimYD The behavior oftungsten oxidesinthe presence of copper during hydrogen reduction J Alloy Comp 2006419262ndash6

[19] Kim DG Min KH Chang SY Oh ST Lee CH Kim YD Effect of pre-reduced cuparticles on hydrogen-reduction of Wndashoxide in WO3ndashCuO powder mixturesMater Sci Eng A 2005399326ndash31

Fig 10 Effect of reduction time on different ratios of W to Cu a) W-20 wtCu b)W-30 wtCu





the effects of the reduction temperature and H2 1047298ow rate on the

hydrogen reductionrate andcrystallite size of theWndashCu powderwerealso investigated The present work has shown that the wet-chemical

process can produce well-dispersed WndashCu powders with mean

particle size of about 100 nm

2 Experimental

21 Preparation of W ndashCu powders

Ammonium metatungstate and copper nitrate solutions were 1047297rst

prepared by dissolving corresponding salts in distilled water The

solutions were then mixed according to different stoichiometric ratios

of W toCu(Wndash20 wtCu Wndash26 wtCu andWndash30 wtCu) Complex

solutions were obtained by adding aqueous ammonia precipitant into

the mixed solutions and maintaining the pH value at about 6Precursor powders were obtained by spray-drying the complex

solution at a temperature of about 200 degC The precursor powders

were subsequently calcined at 600 degC followed by reducing in H2 at

800 degC for 1 h to convert into WndashCu powders The height of the

calcined powder bed is about 10 mm dew point and 1047298ow rate of H2

are negative 50 degC and 100 mlmin respectively

22 Characterization

Simultaneous differential thermal analysis and thermogravimetry

(DTA-TG) were carried out on the dried precursor powders The

samples were heated from room temperature to 800 degC at a heating

rate of 10 degCmin under a dynamic air 1047298ow The precursors and the

calcined powders with different ratios of W to Cu as well as the

resulting WndashCu powders were characterized by X-ray diffractometer

(XRD) Grain size of W and Cu in the WndashCu powders reduced atdifferent temperature was calculated according to the Scherrer

equation Particle size and morphology of the precursor powders

the calcined powders and the resulting WndashCu powders were

examined by transmission electron microscope (TEM) and scanning

electron microscope (SEM) Weight loss of the calcined precursors

under different reduction temperatures and H2 1047298ow rate was

measured using a thermal balance to analyze the kinetics of the

reduction process

Fig 1 XRD patterns of the dried precursors with different ratios of tungsten to copper a) W-26 wtCu b) W-20 wtCu c) W-30 wtCu

Fig 2 DTA-TG results of the Wndash

26 wtCu precursors


























powders












































































































Table 1


temperatures



Wndash20 wtCu 2477 2763 3217 1833 2003 2372

Wndash26 wtCu 2015 2356 2878 1952 2291 2845

Wndash30 wtCu 1983 2205 2525 2213 2502 3210



















about 251 kJmol

4 Conclusions












Acknowledgements




References

















ultra1047297


































powders












































































































Table 1


temperatures



Wndash20 wtCu 2477 2763 3217 1833 2003 2372

Wndash26 wtCu 2015 2356 2878 1952 2291 2845

Wndash30 wtCu 1983 2205 2525 2213 2502 3210



















about 251 kJmol

4 Conclusions












Acknowledgements




References

















ultra1047297
























































































Table 1


temperatures



Wndash20 wtCu 2477 2763 3217 1833 2003 2372

Wndash26 wtCu 2015 2356 2878 1952 2291 2845

Wndash30 wtCu 1983 2205 2525 2213 2502 3210



















about 251 kJmol

4 Conclusions












Acknowledgements




References

















ultra1047297

























about 251 kJmol

4 Conclusions












Acknowledgements




References

















ultra1047297











Synthesis and Characterization of W–Cu Nanopowders by a Wet-chemical Method-2011

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Transcript of Synthesis and Characterization of W–Cu Nanopowders by a Wet-chemical Method-2011