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"Glass Defects Related with Heavy

Mineral & Clay Bearing Raw Materials"

Sener YILMAZ , E.Burak IZMIRLIOGLU


Glass Research Center
Glass Trend Istanbul Seminar
4 6 November 2013, Turkey

OUTLINE
Chromite stones originated from sand
Zircon stones originated from feldspar
Quartz-Mullite defects originated from
clay (kaolinite) in sand
Conclusion

Chromite stones originated from sand


Chromite [Fe,Mg) (Cr, Al, Fe)2O4 ] :

occurs especially in ultramafic rocks (i.e.,


peridotite, ophiolite)
has a density of 4.5 - 4.8 g/cm3
has a melting point of 1850 2200 0C

Chromite stones originated from sand


Case: Chromite inclusions in float glass due to
silica sand containing coarse chromite grains.
History:
Silica sand used in float glass batch has been
mined from sandstone deposit.
Chromites were concentrated with quartz in
large amounts during the formation of the
deposit by sedimentation process.

Chromite stones originated from sand

SEM-SEI image of chromite stone defects in float glass

Chromite stones originated from sand


EDS analysis of some chromite stones in float glass
Na2O

MgO

Al2O3

SiO2

Cr2O3

Fe2O3

Chromite (%)

0,34

13,18

7,22

1,92

66,68

10,66

Chromite (%)

0,58

13,44

7,49

3,33

68,6

6,55

Chromite(%)

0,35

12,82

7,74

1,72

66,37

11

Chromite (%)

0,55

13,71

8,16

3,21

69,26

5,11

Chromite stones originated from sand


SEM-SEI images of some rounded chromite grains in silica sand

Chromite stones originated from sand


EDS analysis of some chromites (Mg-Chromites)in sand
MgO

Al2O3

Cr2O3

Fe2O3

Chromite (1)

7.68

16.18

60.94

14.45

Chromite (2)

2.93

12.54

53.75

29.31

Chromite (3)

10.02

22.94

42.32

23.35

Chromite (4)

5.69

13.68

47.31

31.17

Chromite stones originated from sand


Melting Behaviour of A Single Chromite Grain
In Glass Melt

Chromite stones originated from sand


Specifications for chromite in float glass sand
vs.
chromite grains in silica sand (sandstone)
Particle size

(m)
+ 400

Chromite
specification
(Number / ton)
0

Chromite grains
in silica sand
(Number / ton)
20

+ 300

40

300

+ 200

1000

1500

Chromite stones originated from sand


Cure: To remove chromite particles from sand
Reduce product size of sand below to 0.400 mm

Use gravity separation techniques


(i.e., Humphrey Spiral)

Chromite stones originated from sand


Humprey Spiral is the most effective gravity
separation technique for removing of chromite
mineral from sand.

Zircon stones originated from feldspar


Zircon (ZrSiO4):
Its small crytals can be found in all type rocks (igneous,
metamorphic and sedimentary ) as accessory mineral
Its large crytals (up to 1 cm) occur especially in
pegmatites and granites (Nepheline syenite)
Has a density of 4.6 4.7 gr/cm3
Has a melting point of over 2500 0C (It dissociates to
zirconia and quartz over 1550 0C)

Zircon stones originated from feldspar


Case: The brekage of bottles during pressure
tests because of coarse zircon inclusion.
History: Nepheline syenite, like feldspar, supplies
alumina and also provides alkalis that act as a
flux to lower the melting temperature in
glassmaking. It is a kind of feldspathic rock.

Zircon stones originated from feldspar


SEM-SEI image and EDS analysis of zircon
inclusions in green bottle samples.
Formula

Formula

Zircon stone (%)

SiO2

31.11

ZrO2

68.89

Zircon stone (%)

SiO2

30.88

ZrO2

69.12

Zircon stones originated from feldspar


Mineralogical investigation results show that
feldspar contains:
~ 20 free zircon grains, which is coarser than
0.500 mm, per 1 kg feldspar
Grain size distribution of zircon in feldspar is between
0.4 0.7mm (mostly coarser than 0.5 mm)

Zircon stones originated from feldspar


Zircon stone inclusions due to feldspar which is
mined from nepheline syenite deposit.
a

a) Free zircon grains


b) Nepheline syenite rock fragments

Zircon stones originated from feldspar

X-ray elemental mapping of coarse zircon grains

Zircon stones originated from feldspar


Cure:

The most effective and economic way is

to reduce product size of feldspar


below to 0.400 or 0.500 mm to prevent
coarse zircon grains from entering furnace
with feldspar.

Quartz Mullite defects originated


from clay (kaolinite) in sand
Kaolinite [Al2Si2O5(OH)4]:

One of the member of kaolinite group (kaolin


minerals)
Formed by the alteration of feldspars in granites or
extrusive igneous rocks either hydrothermally or by
weathering
On heating up to 1000 C, the mullite phase is
formed

Quartz Mullite defects originated


from clay (kaolinite) in sand
Case: Quartz Mullit inclusions in float glass
ribbon due to high content clay (kaolinite) in glass
sand.
History: Glass sand produced from sandstone
which contains high content kaolinite (~ 5 % wt).

Quartz Mullite defects originated


from clay (kaolinite) in sand
Stone
(Quartz)
(%)

Knot
(Mullite)
(%)

Na2O

0.53

6.72

Al2O3

0.66

13.4

SiO2

98.68

79.0

K2O

--

0.49

CaO

0.13

--

Microanalysis of quartz mullite inclusion

Quartz Mullite defects originated


from clay (kaolinite) in sand

Thermal Behaviour of Kaolinite Clays

Quartz Mullite defects originated


from clay (kaolinite) in sand
Chemical composition of glass sand (% wt)
Al2O3

SiO2

Na2O
+ K2O

Fe2O3

TiO2

CaO + MgO

L.O.I

2.1 2.3

95 - 96

0.2 0.8

0.1

0.05

0.2

0.6 0.9

Mineralogical composition of glass sand (% wt)


QUARTZ

CLAY

FELDSPAR

OTHERS

93 %

5%

1%

1%

Quartz Mullite defects originated


from clay (kaolinite) in sand
Mineralogical analysis shows that glass
sand is a kind of kaolinitic sand,
NOT
a feldspathic sand.

Quartz Mullite defects originated


from clay (kaolinite) in sand

SEM image of fine kaolinite particles coating on


quartz grains

Quartz Mullite defects originated


from clay (kaolinite) in sand
Cure: To remove clay particles from sand, some
mineral processing techniques can be applied in
the plant.These techniques are namely,

Scrubbing

Attrition scrubbers

Classification & Separation

Hydrocylones

Drying & Screening

Vibrating Sieves

Conclusion
Apart from incompletely melted quartz
grains, "heavy minerals" and "clays" may
also precipitate the formation of stones
that originate in the glass raw materials.
The most harmful minerals are especially
those

Conclusion (1)
that dissolve in the glass at a slower
rate than the quartz ,

Conclusion (2)
that are transformed into chemically
more resistant phases at high
temperatures (kaolinite
mullite)

Conclusion (3)
That release low-solubility components
into the glass during their dissolution
( chromite
escolaite)
( zircon
zirconia + quartz)

THANK YOU !

Questions?