JOURNAL OF MATERIALS SCIENCE LETTERS 14 (I995) 1574-1576
Optical characterization of black glasses from the ZnO-CdO-Al203-Si02
composition system
MA. E. ZAYAS
Centre de Investigation on Ffsica, Universidad de Sonora, Hermosillo, Sonora, Mexico
H. MARQUEZ
Division Ffsica Aplicada, Departamento de Optica, CICESE, Ensenada BC, Mexico
E. RIVERA
Calipo S.A., Departamento de I+D, Ensenada, BC, Mexico
J. MA. RINCON
Department of Materials Science Institute E. Torroja de Ciencias de la Construccibn CSIC, 28033 Madrid, Spain
In recent years glasses with high transmission in the
near infrared have become important for different
technological applications. Several optical devices
(high energy polarization devices, laser aligners,
autocollimators, etc.) use black glass plates as
transmission radiation windows in the near infrared
and absorbers in the visible spectrum.
Usually, by using conventional glass matrices such
as phosphate, borate, borosilicate and silicate, black
glasses with addition of different colouring agents for
controlling optical transmission [1] have been
obtained.
Recently, black glasses in the CdO-A1203-SiO2
system useful for optical devices have been investi-
gated [2]. New families of cadmium glasses have
been reported in the ZnO-CdO-A1203-SiO2 system
containing 12 wt % A1203 [3-5]. It is the aim of this
letter to show the influence of composition on the
spectral transmittance of black glasses in a ZnO-
CdO-A1203-SiO2 glass matrix with copper, manga-
nese and selenium additions.
A wide range of glasses with different composi-
tions were prepared from ZnO, CdO and SiO2
covering the entire ZnO-CdO-AlzO3-SiO2 system
[6]. Several glasses from this composition system
have been prepared with similar CuO, MnO2 and Se
additions (Table I). In addition, the 20ZnO'50CdO-
30SIO2 (wt%) composition with different CuO,
MnO2 and Se additions was prepared.
The raw materials used were reactive grade oxides.
In order to homogenize the original mixture, ball-
milling was used. Melting of the mixtures was
carried out in alumina-silica crucibles in a Kanthal
electric furnace at 1400-1450°C, followed by
annealing and cooling heat treatment at 200 °Ch -1.
The final appearance of the glasses is described in
Table I.
The spectral transmission was measured in the
200-2600nm range using a Perkin-Elmer 330
spectrometer with a 4 mm thick plate. The plate
was embedded into Canada Balsam and glued to a
glass holder. The sample was polished on both planes
1574
to A/2 flattening, which is useful for these kinds of
measurements.
To determine chromatic coordinates the glass
samples were powdered and measured in a Perkin-
Elmer colorimeter used A, D illuminant, which gives
results in good agreement with CIE (Commission
Internationale de l'Eclairage), with a chromaticity
diagram for the tri-stimulus chromaticity shape,
namely X red, Y green and Z blue. The fracture
surface of these glasses was observed by replica
method by transmission electron microscopy (TEM)
in a Philips EM-300. Finally, to determine the
average Fullman radius of phase separation droplets
an image semi-automatic analyser (Zeiss Morphomat-
30) was used.
The spectral transmittance is shown in Fig. 1 for
glasses BG3-BG9. From this figure it can be seen
that an increase of ZnO and CdO percentages and
decrease of the SiO2 concentration (samples 3 and 9)
gives rise to high transmission in the 1400-2600 nm
near infrared interval and absorption in the full
TABLE I Batch compositions (wt%) of ZnO-CdO-SiO 2 glasses
with additions of CuO, MnO2 and Se
Sample ZnO CdO SiO 2 CuO MnO2 Se Appearance
BG3 20 60 20
BG4 20 50 30
BG5 20 30 50
BG6 10 40 50
BG7 l0 50 40
BG8 10 60 30
BG9 30 40 30
BG4CE1 20 50 30
BG4CE2 20 50 30
BG4CE3 20 50 30
BG4CE4 20 50 30
BG4CE5 20 50 30
BG4CE6 20 50 30
5 2.5 2.5 Black
5 2.5 2.5 partly
Green a
5 2.5 2.5 Green ~
5 2.5 2.5 Black
5 2.5 2.5 Black
5 2.5 2.5 Black
5 2.5 2.5 Black
5 - Metal
Black
- 5 - White
Ivory
- - 5 Violet
5 5 - Black
5 - 5 Metal
Black
- 5 5 Brown a
aTransparent.
0261-8028 © 1995 Chapman & Hall