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Encapsulating MAl2 O4 :Eu2+ , Dy3+ (M = Sr, Ca, Ba) phosphors with triethanolamine
to enhance water resistance
Ping Ting Ji, Xiang Ying Chen , Ye Qin Wu
School of Chemical Engineering, Anhui Key Laboratory of Controllable Chemistry Reaction & Material Chemical Engineering, Hefei University of Technology, Hefei, Anhui 230009,
PR China
a r t i c l e i n f o a b s t r a c t
Article history: Traditional aluminates phosphors with persistent luminescence are chemically unstable to water or
Received 21 August 2011 moisture. Thus, how to improve the water-resistance of these phosphors is becoming a key issue in their
Received in revised form practical applications. In this work, a series of alkaline earth aluminate phosphors including MAl2 O4 :Eu2+ ,
29 September 2011
Dy3+ (M = Sr, Ca, Ba) have been prepared by a co-precipitation synthesis and postannealing approach,
Accepted 18 October 2011
using 8-hydroxyquinoline and sodium oxalate as precipitants. The samples before and after encapsula-
Available online 23 October 2011
tion were well characterized by means of XRPD, FESEM, FT-IR, TGA-DTG and PL techniques as well as
water resistance measurements. The precipitants involved can react with Al3+ and Sr2+ (or Ca2+ , Ba2+ ) to
Keywords:
Aluminate phosphors
form complex compounds in aqueous solution, which further convert into porous phosphors by postan-
Encapsulation nealing method under reducing atmosphere. Next, triethanolamine encapsulation at room temperature
Triethanolamine was conducted onto their surfaces to improve the water resistance. The results reveal that the encapsu-
Water resistance lation of aluminate phosphors with triethanolamine can effectively enhance the water resistance, and
Co-precipitation minimally affect on persistent phosphorescence.
2011 Elsevier B.V. All rights reserved.
0169-4332/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.10.098
P.T. Ji et al. / Applied Surface Science 258 (2011) 18881893 1889
* ** +
$ * +
* +
#
+
+
* # +
* * *
Intensity (a.u.)
** $ * *** *** ++ # # + +
+
(b) * ** * (b) # # + + ++
* ** *
# $ * * ++ # +
Intensity (a.u.)
* *** # # #
* *
* * * +
+ +
# +
* * * * ** + +
#* ** * * ** + + +
(a) *
* ** ** * ** * * + ** +
+ + + +
* * * * ** (a) ++ ** +
10 20 30 40 50 60 70
10 20 30 40 50 60 70
2 (degree)
2 (degree)
Fig. 1. XRPD patterns of SrAl2 O4 :Eu2+ , Dy3+ phosphors before (a) and after (b) being
encapsulated with triethanolamine. Notes: * = hexagonal SrAl2 O4 (JCPDS Card No. Fig. 3. XRPD patterns of BaAl2 O4 :Eu2+ , Dy3+ phosphors before (a) and after (b) being
34-0379); # = cubic SrAl2 O4 (JCPDS Card No. 40-0025); $ = anorthic Al(OH)3 (JCPDS encapsulated with triethanolamine. Notes: + = hexagonal BaAl2 O4 (JCPDS Card 17-
Card No. 72-0623). 0306); # = monoclinic -Ba(OH)2 (JCPDS Card 44-0585); * = unidentied peaks.
2. Experimental
by precipitation, while organic layers cover phosphors through
coordination combination. However, as much as we know, there All chemicals are of analytical grades and used as received
are few reports on encapsulating aluminate phosphors with tri- without further purication. The water-resistance measurements
ethanolamine to enhance water-resistance. were carried out by simply adjusting the dosage of triethanolamine
Recently, we prepared a series of MAl2 O4 :Eu2+ , Dy3+ (M = Sr, (0.5 mL, 1.0 mL and 1.5 mL) at room temperature.
Ca, Ba) phosphors by hydrothermal and Pechini-type solgel
approach [18,19]. As the extension of these works, we herein use 2.1. Typical procedure for preparing SrAl2 O4 :Eu2+ , Dy3+ phosphor
8-hydroxyquinoline and sodium oxalate as precipitants to prepare by a co-precipitation synthesis and postannealing approach
aluminate phosphors by a co-precipitation synthesis and postan-
nealing approach. It should be noted that triethanolamine, for the According to the nominal composition of SrAl2 O4 :Eu0.01 2+ ,
rst time, was chosen as encapsulation reagent for phosphors to Dy0.02 3+ , Sr(NO3 )2 (3 mmol), Al(NO3 )3 9H2 O (6 mmol), Eu(NO3 )3
improve the water-resistance. Besides, photoluminescent proper- (0.03 mmol), and Dy(NO3 )3 (0.06 mmol) were rst dissolved in
ties before and after encapsulation were briey studied by emission 60 mL deionized water to form clear solution. Then, Na2 C2 O4
technique. (3 mmol) pre-dissolved in 20 mL deionized water and 8-
hydroxyquinoline (18 mmol) pre-dissolved in 20 mL absolute
ethanol were poured into the above solution, rapidly giving rising
to yellowish-green precipitates. After being magnetically stirred
& for ca. 3 h at room temperature, the above precipitates was ltered,
% &
washed with distilled water and absolute ethanol for several times,
and then dried under vacuum at 80 C for 10 h. Next, the dry precip-
& & itates were further postannealed in a horizontal tube furnace under
& reducing atmosphere (20% H2 + 80% Ar) at 1100 C for 3 h to obtain
&
$ & SrAl2 O4 :Eu2+ , Dy3+ phosphor.
Intensity (a.u.)
Fig. 4. FESEM images of the phosphors before encapsulation: (a and b) SrAl2 O4 :Eu2+ , Dy3+ ; (c and d) CaAl2 O4 :Eu2+ , Dy3+ ; (e and f) BaAl2 O4 :Eu2+ , Dy3+ .
2938
Dy3+ phosphor under present treatment. Meanwhile, similar FT-
1458
IR results occur towards CaAl2 O4 :Eu2+ , Dy3+ and BaAl2 O4 :Eu2+ ,
Transmittance %
1040
1400
1000
Dy3+ phosphors before and after being encapsulated with tri-
648
ethanolamine, as shown in Figures S1 and S2, respectively.
786
Due to the lone pairs in nitrogen atom (pKa = 7.8), tri-
852
(a) ethanolamine can readily hydrolyze to produce OH or protonate
in aqueous solution, as shown in Eqs. (1) and (2). Therefore,
when dropping minor amount of HCl solution into the mixture of
1458
SrAl2 O4 :Eu2+ , Dy3+ phosphor and triethanolamine to make the nal
pH ca. 12 in absolute ethanol, protonated triethanolamine comes
648
786
forth, concurrently with the formation of Al(OH)3 , which can push
852
the equilibrium to the forward direction in Eq. (3).
4000 3000 2000 1000 + H2 O RN+ + OH
RN (1)
-1
Wavenumbers cm + +
+ H RN
RN (2)
Fig. 5. FT-IR spectra of SrAl2 O4 :Eu2+ , Dy3+ phosphor before (a) and after (b) being
SrAl2 O4 + H2 O Sr2+ + 2OH + Al(OH)3 (3)
encapsulated with triethanolamine.
0 13
100
(b) 12 (a)
-5
95
11
-10 90
exothermic
TGA (wt %)
10
pH
-15 32.5% 85 9
(b)
80 8 (d)
-20
(c)
75 7
-25
272 (a) 70 6
522 438
a1 before encapsulation b1 before encapsulation
(a) (b)
a2 after encapsulation b2 after encapsulation
b1
a1
Intensity (a.u.)
Intensity (a.u.)
b2
a2
400 450 500 550 600 650 400 450 500 550
wavelength (nm) wavelength (nm)
c1
Intensity (a.u.)
c2
Fig. 8. Emission spectra of phosphors before and after being encapsulated with triethanolamine: (a) SrAl2 O4 :Eu2+ , Dy3+ ; (b) CaAl2 O4 :Eu2+ , Dy3+ ; (b) BaAl2 O4 :Eu2+ , Dy3+ .
P.T. Ji et al. / Applied Surface Science 258 (2011) 18881893 1893