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COLOURED
Alicia DURAN
z Instituto de Cer~mica y Vidrio (CSIC), Arganda del Rey, Madrid, Spain 2 CIDA, Cristalerla Espahola, S.A. Avil$s, Asturias, Spain
Glass coloured coatings of M,Om-NpOq-SiO2 (M, N = Fe, Co, Ni, Mn, Cr) have been prepared on soda-lime-silica flat glasses by the sol-gel route using the dip-coating technique. The optical properties of these films were investigated by spectrophotometry and the optical parameters obtained allowed the colouration mechanism acting in each case to be determined as well as a comparison to be made with the parameters on the single TMO coloured films. Colour coordinates were calculated in every case. On the other hand coatings have been prepared consisting of two different single TMO films. The corresponding mixed coatings were compared with these double films, showing different behaviours and widening the colour spectrum of glass TMO coatings.
1. Introduction
T h e p r e p a r a t i o n of c o l o u r e d glass c o a t i n g s resuits in an interesting a n d p r o m i s i n g a p p l i c a t i o n of the s o l - g e l technique. D i f f e r e n t colours with v a r y i n g hues a n d intensities can be o b t a i n e d using single or m i x e d t r a n s i t i o n m e t a l oxides ( T M O ) . This w o r k c o m p l e t e s a research p r o g r a m on glass c o l o u r e d coatings in the system M n O m - S i O z ( M = t r a n s i t i o n metal). I n p r e v i o u s articles [1,2] the single c o l o u r i n g oxides series was studied, here we are c o n c e r n e d with the m i x e d T M O c o l o u r i n g b e h a v i o u r o n the s a m e glass silica matrix. T h e m a i n a i m is to c h a r a c t e r i z e the c o l o u r of the c o a t e d glasses, to s t u d y the c o l o u r i n g m e c h a Table 1 Coating 10Fe-5Cr 10Fe-10Co 5Fe-10Co 10Co-10Ni 10Co-20Ni 15Co-5Cr 5Cr-25Ni 5Cr-15Mn 10Cr-10Mn Composition (mol %) Fe203 10 10 5 CoO 10 10 10 10 15 10 20 25 NiO
2. Experimental
T h e s t u d i e d c o m p o s i t i o n s , b e l o n g i n g to the syst e m x M n O m. y N p O q . (100 - x - y ) S i O z, with M a n d N = Fe, Co, Ni, Cr, M n , are shown in table 1. Starting s o l u t i o n s were p r e p a r e d b y m i x i n g T E O S , e t h a n o l , distilled w a t e r a n d nitrates o f the c o r r e s p o n d i n g T M O , using HC1 a n d acetic a c i d as catalysts. F i n a l solutions s h o w e d suitable p r o p e r ties of viscosity a n d stability.
Cr203
MnO
SiO2 85 80 85 80 70 80 70 80 80
5 5 5 10
15 10
495
Thin glass films were obtained on microscopy slides of soda-lime-silica glass by dip-coating at different withdrawal rates (6-60 cm/min), dried at 6 0 C for 30 rain, and later heat-treated at 5 0 0 C for 1 h. On the other hand, coatings consisting of two different single T M O films were prepared by repeating the same process for each layer. Four pairs of single T M O coatings were chosen combining different intensities and colouring mechanisms: Fel0 + Cr5; Col0 + Ni20; Co15 + Cr5 and Crl0 + Mnl0. The thickness of the films was measured using Talystep equipment and the optical absorption spectra were obtained using a Perkin Elmer ~-9 spectrophotometer.
cal mixture of single oxides but the excitation purity P is higher than the theoretical one, fig. la. The coloring mechanism acting in this case is a combination of absorption and scattering.
Homogeneous coloured coatings were obtained from all the mixed T M O solutions, the film thicknesses varying between 250 and 700 nm depending on the type and concentration of the T M O pair added. The colour parameters of the coated samples were calculated for standard Iluminant C and CIE observer 1931. The spectrophotometric measurements were taken at normal incidence, eliminating the contribution of the glass substrate. No correction was made for the difference between the coating and substrate refraction index.
3.1.2. Fe- Co coatings 10Co coatings behave as pure absorption colours while 5Fe and 10Fe colours also show a scattering contribution. Important differences appear between the selected mixtures, 5 F e - 1 0 C o and 10Fe-10Co: an absorption colouring mechanism prevails in the first case while a typical scattering spectrum is exhibited by the coating containing 10 mol% of Fe203, fig. 2a. On the other hand, colour dominant wavelengths separates from 571 to 579 nm while purities show great differences for an equivalent thickness, fig. lb. The Co effect is only observed in 5Fe composition by a strong diminution of purity, since colour vectors are almost opposite. 2td shifts to wavelengths longer than that corresponding to Fe coatings which suggests a coprecipitation of Fe and Co oxides. 3.1.3. Co-Ni coatings Single oxide colours result in pure absorption ones, although a small scattering contribution is observed for 20Ni films. Since both colour vectors are almost opposite, oxide mixtures should cause a diminution of the purity and a displacement of the colour to the grey zone. 10Co-10Ni coatings show a dominant wavelength of )t o -- 569 nm, low purity; ( P < 2%) and light grey hues, fig. lb. For 10Co-20Ni, higher values are detected, 2td = 576 nm and P - 10%, with greyish-brown colours resulting. The colour behaviour of both mixed coatings does not agree with those corresponding to theoretical mixtures, scattering effects being observed in transmittance spectra. 3.1.4. Co- Cr coatings A 15Co-5Cr composition has been chosen. Single 15Co and 5Cr coatings show pure absorption colours with well defined dominant wavelengths, 479 and 571 nm, and purities around 5% for thickness of 400 nm.
3.1.1. Fe- Cr coatings Single coatings containing Fe and Cr show mixed absorption scattering and pure absorption mechanisms respectively. In the 10Fe-5Cr mixed coating, the colour dominant wavelength, ?td, coincides with that corresponding to the theoreti-
496
a
.40C ^
23%
s6o
=,%
,m
)
5~
.360
5: 5~ .34C 5; 51
.320 4~
4! 4; ,30(;
.3000
oou -oou
.3 I 0 0
-o,q~./
-ocu - o lU .3200
-.330 0
550
23%
560
30%
5"lo
Fig. 1. Colour coordinates of mixed TMO coatings. (a) Fe-Cr and Cr-Mn coatings, (b) Fe-Co and Co-Ni coatings, (c) Cr-Ni and Co-Cr coatings.
A. Duran et aL
497
ioo 8o
60 40
20
5Fe-lO C o - - ~
ioot
/.~.~.~'~
.,~._ 10 Fe- I0 Co
8O 6040-
15Co-5Cr
/ /
4%o
20-
d3 o /
o "'
I,--
a
560
odo
~
800 ~
I--
b
o 3oo
30o
~6o
460
560
660
760
eoo
,oo I
80
,oo
80-
-25Ni
60 40 20
C
I I / I
604020.
0
~SCr-
10 Mn
A
~
//
u
300
400
500
~[nm]
600
700
800
300
400
500
600
~[nm]
700
800
Fig. 2. Transmittance spectra of mixed TMO coatings. (a) Fe-Co coatings, (b) Co-Cr coatings, (c) Cr-Ni coatings, (d) Cr-Mn coatings.
Mixed coatings, of an intense olive green colour, exhibit a }k d = 575 nm and high purities between 25 and 45% for thickness from 160 to 500 nm, fig. lc. The resulting colour is not related to the addition of pure single colours and the absorption spectrum fig. 2b allows it to be identified as a scattering colour.
purity is practically equal to the theoretical value, fig. lc. The absorption spectrum, fig. 2c, suggests an ionic colouring mechanism with a small scattering contribution.
3.1.5. Cr-Ni coatings 5Cr-25Ni coatings are the only mixed coatings studied in which the colour is similar to that of the theoretical mixture. The dominant wavelength is slightly shifted to the Cr colour vector but the
3.1.6. Cr-Mn coatings The compositions selected, 5 C r - 1 5 M n and 10Cr-10Mn, combine pure absorption and mixed absorption-scattering colours, with Ad = 571 and 584 nm respectively. Both mixed coatings possess the same dominant wavelength, Ad = 577 nm, although colours differ in purity and intensity, fig. la. The darkest
498
ones correspond to 10Cr-10Mn composition in which a greater scattering contribution is detected, fig. 2d, justifying the higher colouring power.
80,.
60.
; k'-Ni20+ClO
40.
2o.
'.' z
0 300 IOOi
600
700
800
xEm] Cr5+C015-7
--Col5+Cr5 60
t---
80
3.2.1. FelO + Cr5 coatings The superposition of two different single coloured films of 10Fe and 5Cr produces colours with a unique Xd, identical to that of 5Cr coatings, without respecting the colour addition rules. When the order of the films is 5Cr over 10Fe, the purity obtained is similar to the theoretical value; if the order of the coatings is reversed, higher purities result, fig. 4a, while the absorption band corresponding to Cr 6+ ions becomes more intense. 3.2.2. lOCo-20Ni coatings In this case, light grey colours result, with low purities and variable dominant wavelengths. In general, the colour of the coatings 10Co i + 20Nij does not agree with that of the theoretically identical 20Nij + 10Coi coatings. When the first coating is 10Co, the final colour is similar to the theoretical one with shift to 10Co wavelength; instead, if the order is 10Co over 20Ni, Xd approaches that of 20Ni. Fig. 3a shows the spectra of two equivalent double coatings. This ~k d shift could indicate a precipitation of oxide particles from the first film, possibly caused by the double heat treatment. After treating several samples at 500C for 2 h, a cut-off shifting to longer wavelength was detected in coatings with NiO concentration higher than 20 mol%, support-
4O
b
5OO
46o
56o
660
700 '
800
Fig. 3. Transmittance spectra of double coloured coatings. (a) Co + Ni coatings, (b) Co + Cr coatings.
ing the previous hypothesis. In 10Co and 15Co samples this effect was not detectable.
3.2.3. 15Co + 5Cr coatings The colour of these double coatings cannot be obtained by the addition of the single coating colour vectors. As a common characteristic, the colour is determined by the first film, although the cobalt effect is less than that of chromium and always less than the theoretical effect. 15Co acts as the first film shifting the dominant wavelength slightly and diminishing purities.
A. Duran et aL
499
b
a
Y
14/~ 550 ISP/a~ 0 570
Y 5,~ 9%
550
560
14%
5TO
.3000
.3150
.3300
.3 4 50
.3000
.3150
.3300
Y 54o
-,~
/ \
7-.
q
"~
.3eoo " ~
T E R[] E X P E R ~ HO
lOCr I~
530
5%
.3400520
510
500
Fig. 4. Colour coordinates of double TMO coatings. (a) Fe + Cr coatings, (b) Cr + Co coatings, (c) Cr + Mn coatings.
500
Experimental Xd results are longer than theoretical Xd, but the luminuous transmittance Y
- In mixed T M O coatings a scattering colouring mechanism predominates, which seems to be emphasized by coprecipitation of the single oxides. The resulting colours are more intense and saturated than the theoretical ones. - In double coatings, the deposition order of coatings influences the final colour, this effect being more apparent in Ni and Cr coatings. In Ni containing films, the heat treatment provokes a rising of the scattering band. In Cr coatings, the absorption band corresponding to Cr 6+ becomes more intense. - N o redox interaction appears in any of the studied T M O pairs. - The association of two T M O in mixed coatings or in double coatings allows the colour gamut of glass coloured coatings to be widered although the substractive colour mixture rules are not respected.
4. C o n c l u s i o n s -
References
colour of the coatings prepared in mixed coatings or in double correspond to that obtained by single colours.
[1] A. Durhn, J.M. Fermindez Navarro, P. Casariego and A. Joglar, J. Non-Cryst. Solids 82 (1986) 391. [2] A. Durhn, M. Maz6n, A. Joglar and J.M. Fernandez Navarro, Riv. Staz. Sper. Vetro 16 (1986) 6, 59.