Title of Invention

A PROCESS FOR PRODUCING AN INORGANIC DOPED-ZIRCON PIGMENTS

Abstract A process(10) for producing an inorganic doped-zircon pigment includes calcining(30) a base mixture comprising raw plasma-dissociated zircon, a chromophore, and at least one mineralizer, to produce a raw pigment. The raw pigment is refined (34) to obtain an inorganic doped-zircon pigment.
Full Text THIS INVENTION relates to the production of inorganic doped-zircon pigments. It
relates in particular to a process for producing an inorganic doped-zircon pigment.
According to the invention, there is provided a process for producing an inorganic
doped-zircon pigment/which process includes
calcining a base mixture comprising raw plasma-dissociated zircon, a
chromophore, and at least one mineralizer, to produce a raw pigment; and
refining the raw pigment to obtain an inorganic doped-zircon pigment.
By 'raw plasma dissociated zircon or PDZ' is meant PDZ that has been obtained
directly by means of plasma dissociation, ie without any treatment thereof between
the plasma dissociation of the zircon and the mixing of the resultant PDZ with the
chromophore and the mineralizer, being effected. In particular, the process is
characterized thereby that the raw PDZ is not subjected to any milling and/or any
chemical treatment prior to its use in forming the base mixture.
The raw PDZ may be that obtained by generating a high temperature plasma zone,
and feeding particulate zircon, ZrSiO4, into the plasma zone, thereby to dissociate
the zircon into the raw PDZ. The generation of the plasma zone may be by means
of a non-transfer arc plasma, rather than by means of a transfer arc plasma. More
particularly, the high temperature plasma zone may be provided by means of a
plasma flame generated by at least one non-transfer arc plasma gun. The zircon
may be allowed to free fall through the plasma zone to achieve the dissociation into
the raw PDZ, whereafter the raw PDZ may be quenched in a quench zone below the
plasma zone. Preferably, three non-transfer arc plasma guns, arranged in a star
fashion (when seen in plan view) with their operative ends being downwardly
inwardly directed, may be provided, with the zircon then being allowed to free fall
centrally through the resultant combined plasma zone.
The process for treating the zircon to produce the raw PDZ may thus be in
accordance with WO 96/26159, which is hence incorporated herein by reference
thereto.


Furthermore, the treatment of the zircon to produce the raw PDZ may form part of
the process of the present invention.
The chromophore or colour-determining agent, when it is desired to obtain a yellow
pigment, may be sodium molibdate or may be praseodymium-based, eg
praseodymium oxide, carbonate or oxalate; when it is desired to obtain a blue
pigment, it may be vanadium-based, eg it may be ammonium metavanadate or
vanadium pentoxide; when it is desired to obtain a pink pigment, it may be iron-
based, eg it may be iron oxide or iron sulphate.
During the calcination of the base mixture, the chromophore, or a transient
compound or an ion derived therefrom, becomes entrapped within and/or around the
zircon lattice, thereby forming the pigment having the desired colour.
The mineralizers, whose function it is to reduce the temperature at which the
reaction of the chromophore with the zircon lattice, ie the calcination reaction,
occurs, or to catalyze the calcination reaction, may be an alkali metal halide,
particularly an alkali metal fluoride, any other alkaline mineralizer such as (NH4)2SO4
or Na2SO4, or a combination of two or more of these.
The process may include forming the base mixture by mixing the raw PDZ, the
chromophore and the mineralizer. The raw PDZ, chromophore and mineralizer are
preferably mixed sufficiently so that the base mixture is a homogeneous blend.
The calcination of the base mixture may be effected in an air furnace. The
calcination temperature may be from 800°C to 1300°C.
The refining of the raw pigment may include washing, comminuting and drying it, to
obtain the refined inorganic doped-zircon pigment.
The invention will now be described in more detail with reference to the
accompanying diagrammatic drawing which depicts a simplified flow diagram of a


process according to the invention for producing an inorganic doped-zircon pigment,
and with reference to the subsequent non-limiting examples.
In the drawing, reference numeral 10 generally indicates a process according to the
invention for producing an inorganic doped-zircon pigment.
The process 10 includes a plasma reactor or plasmatron 12 which is in accordance
with WO 96/26159 (which is incorporated herein by reference thereto) and
comprises three non-transfer arc plasma guns, arranged in a star pattern (when
seen in plan view) with their operative ends being downwardly inwardly directed. In
use, the guns generate a central high temperature plasma zone which is at a
temperature of at least 1800°C. A zircon feed conduit is arranged so that zircon can
be allowed to free fall centrally through the plasma zone, thereby to be dissociated
into raw PDZ. A quench zone, in which the raw PDZ is quenched rapidly to below
500°C, is provided below the plasma zone.
A zircon feed line 14 leads into the plasma reactor 12, while a raw PDZ withdrawal
line 16 leads from the reactor 12.
The line 16 leads into a mixer 20, with a mineralizer addition line 22, as well as a
chromophore addition line 24, leading into the mixer. In the mixer, raw PDZ,
mineralizers and a chromophore are mixed into a homogeneously blended base
mixture.
A base mixture withdrawal line 26 leads from the mixer 20, into a calcination furnace
30. The calcination furnace 30 is typically an air furnace. In the furnace, the base
mixture is calcined at 800°C to 1300°C, thereby to cause the chromophore to be
trapped in or around the crystal lattice of the zircon.
A raw pigment line 32 leads from the calcination furnace 30 to a refining stage 34
where the raw pigment is washed, comminuted and dried.
An inorganic doped-zircon pigment withdrawal line 36 leads from the stage 34.


Raw PDZ produced by dissociating zircon sand in the non-transfer arc plasmatron
12 at an average conversion rate of 90% and with a mean particle size of 108 urn
(d50, as determined by a Sedigraph 5100 particle size analyzer) was used as starting
material in the examples hereunder. In the examples, two samples of this raw PDZ
were, in accordance with the invention, used directly as feed material to the
calcination furnace 30, without milling and/or chemical treatment, to produce Pr-
yellow and V-blue pigments by using vanadium pentoxide (V2O5) and praseodymium
oxide (Pr6O11) respectively as chromophore.
For each of these colours, three control samples of the same 108 urn PDZ were
milled down to different particle sizes by means of a wet milling process in a MMS
Series RAPID MILL with a 300 cc porcelain milling jar using ytria-stabilized zirconia
milling media by applying the following method: For Pr-yellow pigments, the three
PDZ control samples were milled down to a d50 of 3.5 µm, 6.0 µm and 8.2 µm
respectively (see Table 1) as determined by a Sedigraph 5100 particle size analyzer.
For V-blue pigments, the three PDZ control samples were milled down to 3.5 urn, 6.0
urn and 8.9 urn respectively (see Table 2).
The PDZ samples were mixed with the required chromophore (Pr6O11 for the yellow
pigments and V2O5 for the blue pigments)and mineralizers as specified in the
examples, in a Y-cone tumbler mixer and thereafter calcined at the temperature as
specified, to produce pigments. After calcining, the pigments were washed in boiling
aqueous hydrochloric acid (HCI) to remove any excess mineralizer and
chromophore, ie the chromophore, which was not incorporated into the zircon crystal
lattice. The pigments of the unmilled PDZ samples (ie according to the invention)
were then comminuted or deagglomerated to a d50 of between 8 - 9 µm for the blue
pigment, and between 6 - 7 µm for the yellow pigment, rendering them suitable for
application to ceramic tiles. A pigment/glaze mixture was prepared, applied to a
Johnson bisque tile with a spray-gun and fired in a muffle furnace at 1080°C with a


soaking time of 5 minutes, after which colour measurements were done with a
Hunterlab colour measuring instrument.
To benchmark the quality of the product in each example, commercially available
stains were used as standards, viz ST 4032 for the yellow pigment and ST 3042 for
the blue pigment. These were obtained from Ferro Industrial Products (Pty) Ltd in
Vulcania, Brakpan, South Africa.
EXAMPLE 1: Praseodymium-yellow Doped-zircon Pigment
An amount of 1.0 mole of unmilled, untreated PDZ was mixed with 0.014 moles
Pr6O11, 0.2 moles NaF and 0.2 moles (NH4)2SO4 in order to ensure a thorough or
homogeneous blend of the colour inducing or determining metal oxide, the
mineralizers and the PDZ. The mixture was then calcined in an air furnace at a
temperature of 1050 °C and for a soaking time of 2 hours after the required
temperature of 1050 °C was reached, to allow the reaction of the praseodymium
oxide and the mineralizers with the dissociated zircon to take place. The resulting
raw yellow pigment was then washed and comminuted to a d50 of between 6 - 7 µm
as measured with a Sedigraph 5100 particle size analyzer. For the control samples,
similar amounts of the milled, treated PDZ were blended, calcined and post treated
as for the unmilled sample, except for the comminution step which was not carried
out.
The results of the colour measurements according to the Hunterlab measurement
technique for both the invention and the control pigment samples are given in Table
1. From these results, the advantage of using unmilled PDZ according to the
present invention as compared to milled and chemically treated PDZ before calcining
can be seen clearly.
In Table 1, the b-values (positive indicates yellow on the tile) for the three control
samples vary from 37.1 (for the 3.5 urn PDZ sample), to 58.8 (for the 8.2 urn PDZ
sample). For the unmilled, untreated PDZ in accordance with the invention, b = 75.8.
Keeping in mind that the higher the b-value, the deeper the yellow appears on the
tile, an increase of 17.0 in b for the pigment using unmilled PDZ as compared to the


best control sample pigment obtained from the 8.2 µm PDZ is significant.
Furthermore, this value of 75.8 compares very favourable with 79.1 for the standard
yellow pigment.
The L-value, which indicates the colour depth of the tile on a scale of 100 for light
(white) and 0 for dark (black), of 78.6 for the unmilled PDZ prior to calcination,
compares very favourably with 78.7 for the standard, while all the controls are lighter
in comparison.

The deviation parameter DE*, which indicates the deviation of the colour hue and
depth from the standard and which is compounded from the primary colour
parameters according to the Hunterlab protocol, is a sensitive parameter to
determine deviations from the standard and which under typical production line
conditions should ideally not exceed 1.0. DE* drops significantly from 20.4 for the
best control sample, to 3.3 for the unmilled PDZ sample prior to calcination, which
clearly emphasizes the advantage of using the unmilled, untreated PDZ in
accordance with the present invention.
EXAMPLE 2: Vanadium-blue Doped-zircon Pigment

The same preparation and production conditions were used as in Example 1.
However, 1.0 mole of unmilled, untreated PDZ was blended with 0.045 moles V2O5,
0.2 moles NaF, and 1.0 mole Na2SO4. The mixture was then calcined in an air
furnace at a temperature of 950°C and for a soaking time of 1 hour after the required
temperature of 950°C was reached, to allow the reaction of the V2O5 and the
mineralizers with the dissociated zircon to take place. In similar fashion to Example
1, the resulting raw blue pigment was washed and comminuted to a d50 between 8 -
9 urn as measured with a Sedigraph 5100 particle size analyzer. For the control
samples the same amount of milled, treated PDZ each were blended, calcined and
post treated as for the unmilled sample except for the comminution step which was
not carried out.
The results of the colour measurements for the V-blue pigments are given in Table 2.

The substantial advantage of using PDZ in the unmilled and untreated condition prior
to the calcining process as compared to the milled and treated PDZ can once again
clearly be seen in the results of the Hunterlab colour measurements. The more
negative the b-value is, the bluer the colour of the pigment appears after application
to the ceramic tile. Amongst the controls b ranges from -6.9 to -3.6 as compared to -
13.5 for the pigment made according to the invention, an improvement of -6.6 with
respect to the best control (Table 2). The fact that the value of -13.5 is still less than

-17.7 for the V-blue standard pigment may be due to the fact that PDZ with a
conversion rate of only 90% was used.
In terms of the L-values not only was a spread of 4.6 from 63.2 to 67.8 observed
between the different control samples, but also the best (for the 8.9 µm sample) is
still 14.3 off the mark with respect to the standard. In contrast, for the unmilled PDZ
pigment an improvement of 9.4 compared to the best control was registered while
being only 4.9 off the mark against the standard.
Observing the deviation from the standard in terms of DE* all the controls deviate
significantly, while the deviation of 6.8 for the unmilled PDZ represents a more
acceptable shift towards the colour standard in view of the conversion rate of 90%
for the PDZ used.
In conclusion, the results for Examples 1 and 2 imply that unmilled plasma
dissociated zircon with a mean particle size of 103 urn produces a pigment very
close to the standard particularly with regard to the b- and the L-values.
EXAMPLE 3: Effect of PDZ Conversion Rate on Pigment Colour
In this example, the influence of the PDZ conversion rate on the colour of the V-blue
and the Pr-yellow pigments was determined. Samples of PDZ, respectively
produced at conversion rates of 95.7, 90.0, 82.4 and 74.7%, were used to produce a
series of Pr-yellow (Table 3) and V-blue (Table 4) pigments each. The same
preparation and production conditions, and the same quantities of raw materials, as
were used in Examples 1 and 2, were used.
In Table 3 the colour measurement results for the Pr-yellow pigments show that the
b-value improves from 65.6 for PDZ with a conversion rate of 74.7%, to 82.3 for PDZ
with a conversion rate of 95.7%. This clearly indicates that the higher the PDZ
conversion rate, the more yellow the colour of the pigment turns out. What is more,
b = 82.3 for PDZ with a conversion rate of 95.7% even surpasses that of the Pr-
yellow standard, a fact supported by its colour depth (L = 77.3), indicating that this


yellow pigment features a deeper hue. In this context, the deviation (DE* = 4.9) from
the standard must be interpreted as a beneficial deviation.
In Table 4 the influence of the PDZ conversion rate on the colour of the V-blue
pigments is shown. Here b increases from -7.8 for PDZ with a conversion rate of
74.7% to -17.9 for PDZ with a conversion rate of 95.7%, giving an improvement of
10.1. Again, b = -17.9 for the PDZ with highest conversion rate equals or betters that
of the V-blue standard.
Thus, the PDZ conversion rate was found to be the most important parameter
influencing the colour of the yellow and blue pigments. Higher conversion rates
consistently result in deeper blue and yellow pigments, respectively, that compare
very favourably with the pigment standards. Apparently a higher PDZ conversion
rate implies that less unconverted zircon is present, which reduces the susceptibility
for colouring of the zircon.



The Applicant has thus surprisingly found that it is possible to produce inorganic
zircon-based pigments directly from PDZ, without first treating the PDZ by milling it
and chemically treating it. These time-consuming and costly steps can thus be
eliminated.
The use of inorganic zircon-based pigments (also known as stains) particularly, but
not solely, in colouring ceramic articles, eg ceramic tiles, is well established.
The present invention thus provides a process whereby such pigments can be
produced more readily and more cost-effectively than has hitherto been the case.

WE CLAIM
1. A process for producing an inorganic doped-zircon pigment, comprising
obtaining a raw plasma-dissociated zircon;
calcining a base mixture of said raw plasma-dissociated zircon, a chomophore
and at least one mineralizer, to produce a raw pigment; and
refining the raw pigment to obtain an inorganic doped-zircon pigment;
wherein said raw plasma-dissociated zircon is not subject to milling between
the plasma dissociation of the zircon and mixing thereof with the chromophore
and the at least one mineralizer.
2. A process as claimed in Claim 1, which includes forming the base mixture by
mixing the raw plasma-dissociated zircon or PDZ, the chromophore and the
mineralizer.
3. A process as claimed in Claim 2, wherein the raw PDZ, chromophore and
mineralizer are mixed sufficiently so that the base mixture is a homogeneous
blend.
4. A process as claimed in any one of Claims 1 to 3 inclusive, wherein the
chromophore or colour-determining agent is selected from the group
comprising sodium molibdate; praseodymium oxide, carbonate or oxalate;
ammonium metavanadate; vanadium pentoxide; iron oxide and iron sulphate.
5. A process as claimed in any one of Claims 1 to 4 inclusive, wherein the
mineralizer is an alkali metal fluoride, (NH4)2SO4 or Na2SO4, or a combination
of two or more of these.
6. A process as claimed in any one of Claims 1 to 5 inclusive, wherein the
calcination of the base mixture is effected in an air furnace.
7. A process as claimed in any one of Claims 1 to 6 inclusive, wherein the
calcination temperature is from 800°C to 1300°C.

8. A process as claimed in any one of Claims 1 to 7 inclusive, wherein the
refining of the raw pigment includes washing, comminuting and drying it, to
obtain the refined inorganic doped-zircon pigment.
9. A process for producing an inorganic doped-zircon pigment, as claimed in any
of Claims 1 to 8, wherein the process further includes:
generating a high temperature plasma zone;
feeding particulate zircon into the plasma zone to dissociate the zircon into raw
plasma-dissociated zircon; and
forming the base mixture comprising the raw plasma dissociated zircon, the
chromophore, and the at least one mineralizer.


A process(10) for producing an inorganic doped-zircon pigment includes
calcining(30) a base mixture comprising raw plasma-dissociated zircon, a
chromophore, and at least one mineralizer, to produce a raw pigment. The
raw pigment is refined (34) to obtain an inorganic doped-zircon pigment.

Documents:

03420-kolnp-2006-abstract.pdf

03420-kolnp-2006-claims.pdf

03420-kolnp-2006-correspondence others-1.1.pdf

03420-kolnp-2006-correspondence others.pdf

03420-kolnp-2006-correspondence-1.2.pdf

03420-kolnp-2006-description (complete).pdf

03420-kolnp-2006-drawings.pdf

03420-kolnp-2006-form-1.pdf

03420-kolnp-2006-form-2.pdf

03420-kolnp-2006-form-3.pdf

03420-kolnp-2006-form-5.pdf

03420-kolnp-2006-international publication.pdf

03420-kolnp-2006-international search authority report.pdf

03420-kolnp-2006-pa.pdf

03420-kolnp-2006-pct others.pdf

3420-KOLNP-2006-ABSTRACT 1.1.pdf

3420-KOLNP-2006-AMANDED CLAIMS-1.1.pdf

3420-KOLNP-2006-AMANDED CLAIMS.pdf

3420-KOLNP-2006-CORRESPONDENCE 1.1.pdf

3420-KOLNP-2006-CORRESPONDENCE 1.2.pdf

3420-KOLNP-2006-CORRESPONDENCE 1.3.pdf

3420-KOLNP-2006-CORRESPONDENCE 1.5.pdf

3420-KOLNP-2006-CORRESPONDENCE-1.4.pdf

3420-kolnp-2006-correspondence.pdf

3420-KOLNP-2006-EXAMINATION REPORT REPLY RECIEVED.pdf

3420-kolnp-2006-examination report.pdf

3420-KOLNP-2006-FORM 1-1.1.pdf

3420-kolnp-2006-form 13.pdf

3420-kolnp-2006-form 18.1.pdf

3420-kolnp-2006-form 18.pdf

3420-KOLNP-2006-FORM 2-1.1.pdf

3420-KOLNP-2006-FORM 3 1.1.pdf

3420-kolnp-2006-form 3.pdf

3420-kolnp-2006-form 5.pdf

3420-KOLNP-2006-FORM-27.pdf

3420-kolnp-2006-granted-abstract.pdf

3420-kolnp-2006-granted-claims.pdf

3420-kolnp-2006-granted-description (complete).pdf

3420-kolnp-2006-granted-drawings.pdf

3420-kolnp-2006-granted-form 1.pdf

3420-kolnp-2006-granted-form 2.pdf

3420-kolnp-2006-granted-specification.pdf

3420-KOLNP-2006-OTHERS 1.1.pdf

3420-KOLNP-2006-OTHERS 1.2.pdf

3420-KOLNP-2006-OTHERS PCT FORM.pdf

3420-kolnp-2006-pa.pdf

3420-kolnp-2006-reply to examination report.pdf

abstract-03420-kolnp-2006.jpg


Patent Number 249431
Indian Patent Application Number 3420/KOLNP/2006
PG Journal Number 42/2011
Publication Date 21-Oct-2011
Grant Date 19-Oct-2011
Date of Filing 20-Nov-2006
Name of Patentee THE SOUTH AFRICAN NUCLEAR ENERGY CORPORATION LIMITED
Applicant Address PELINDABA, 0250 BRITS
Inventors:
# Inventor's Name Inventor's Address
1 SNYDERS, ETTIENNE 743 WEKKER STREET, MORELETAPARK, EXTENSION 5, 0044 PRETORIA
PCT International Classification Number C09C 1/00,C01G 25/00
PCT International Application Number PCT/IB2005/051350
PCT International Filing date 2005-04-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004/3164 2004-04-26 South Africa