WO2016200351A1 - The transparent vetrosa frit which melts at low temperatures having usability with phosphorescence pigments - Google Patents
The transparent vetrosa frit which melts at low temperatures having usability with phosphorescence pigments Download PDFInfo
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- WO2016200351A1 WO2016200351A1 PCT/TR2015/050007 TR2015050007W WO2016200351A1 WO 2016200351 A1 WO2016200351 A1 WO 2016200351A1 TR 2015050007 W TR2015050007 W TR 2015050007W WO 2016200351 A1 WO2016200351 A1 WO 2016200351A1
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- frit
- vetrosa
- transparent
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
Definitions
- This invention is related with frits having low melting temperature, which may be used with phosphorescent pigments and evaluated in vetrosa decoration applications of single-fast-fired glazed wall tiles, transparent, having optimum properties for production method and obtained product and having a wealth of usage.
- the frit based glazes create a different group with the usage advantage of fritted raw materials which are soluble in water without fritting process and with maturation characteristics over a wide temperature range.
- the objectives of fritting are as follows;
- An insoluble glass is formed by combining alkaline carbonhydrates, nitrates, borates, etc. materials soluble in water and melted with other raw materials to form frit.
- the salts soluble within the slurry of glazes being generally prepared with water are disadvantageous because of such a dissolution, resulting a loss of some components which must definetly remain in the system.
- the soluble salts taken by the porous biscuit make the way to crystallisation in corners during drying. These parts burn more intensely and create problems in the glaze.
- soluble salts cause distortion of colours - Slow reacting materials at low temperatures, as barium carbonates, strengthen the fludity when becoming frit components. Stronger fluidifiers increase the performance of fritting and improve the final appeal. - In glaze preparation process, the fritting of raw materials being disadvantageous if used directly eliminates all the relevant undesired consequences. - Frit is the major part of glaze stack. It takes up less space than the corresponding raw materials. Also, it is chemically less active because the decomposition and reaction of the thermal processes had been completed. Therefore, when frit is used the problems of coloring within and under glaze are minimized. The fritted glaze is applied in the form of a thinner layer and so, the product blends better to the spectrum.
- the raw materials will show distinctness in the properties such as depthness, size, shape and hardness, they cause decomposition (segregation) in the batch. As fritting prevents such a tendency, it provides homogenity both in the batch and the end product. Apart from this, colours in the glaze are bright and more pleasant.
- the glaze slurry must be mixed very well before and during the application, otherwise, heavy compounds may precipitate under suitable conditions. Due to pre-melting, large pores which may remain in the glaze and release bubbles are eliminated. On the other hand, being of some raw clay in the fritted glaze batch may overcome some problems like fine sized bubbles.
- frit Two of the most important reasons for using frit are to eliminate the water soluble raw materials access in to the glaze batch and to avoid the possible harm coming from toxic raw materials.
- Solubility All substantially water soluble raw materials must be fritted. These are alkaline salts such as sodium carbonate, potassium nitrate and chloride and common compounds such as lithium oxide, boric acid, and alkaline borade. All of them are strong fluxes and have considerable effects over the physical characteristics of glaze. Calcium carbonate has solubility in water also magnesium oxide and magnesium carbonate are much more soluble in water.
- Solubility of Alkali Silicates As the compunds of alkali and silica are soluble, earth alkaline such as calcium, magnesium, strontium and barium are contributed to the frit harmony in addition to alkali. Lead oxide and zinc alone or with earth alkali compounds stay together for the same reason.
- Aluminium Oxide It is used in alkali not exceeding0.1 or 0.2 moles because it has increasing property of the thermal strength and viscosity at higher rates.
- the Ratio of Alkali to Other RO Elements To keep the water solubility of the end product at a lower level, the total molecular alkali amount in frit may not be more than 50 % of the total RO. Otherwise, some other insoluble alkali such as feldspar might be necessery to join the RO.
- Acidic Components in Frit Practically silica is an essential acidic element in frit generally, with the presence of boric oxide. Apart from this, there are also some other suitable oxides in the system. Silica provides insolubility but to prepare a melt with acceptable fludity at low melting temperature, molecular equivalent should not be under the rate of 1:1.5 and not be over the rate of 1:3. Presence of boric acid increases melting ability and fluidity considerably. To keep solubility at low level, the rate of boric acid should not be more than the rate of the silica by 1:2.
- frit production Some ceramic manufacturers produce frit themselves which they consume in large quantities, they also buy special kinds of frits they used in lesser amount from frit producers.
- the raw materials used in the production are provided directly from the market to be used according to the recipe.
- the flow chart of frit production is given in Figure 2.1. Such a production can be seen as a simple melting process however, there are many parameters which affect this production. If the subjects such as furnace design, refractory, heat transfer and melt chemistry are not understood well, decrease in the melting performance of the furnace might be observed. Weighing is the most basic and important procedure in frit production process. Stored raw materials are feed into weighing silo by a conveyor system and this procedure continues until desired amounts of each raw material are taken. In some cases, raw materials added is taken directly from their bags by weighing. The relevant processes are better performed by computerized systems because it is less likely to make mistakes. All the raw materials should be stored in to silos. After weighing the batch, they are throughly mixed and charged into the frit furnace.
- Mixing procedure consists of two stages. First and basic of these process is mixing the batch when it is dry and second is to mix it in the furnace. Dry mixing before fritting might seem to be easy at first but different characters of batch components do not usually allow such easiness. Raw materials used in fritting indicate distinctness in size distribution, density, particle shape and surface characteristics and accordingly it is hard to obtain homogeneity.
- a completed mixture must consist of all the components at direct proportion. An insufficient mixing time and excessivee loading decrease the quality of the mixture. Insufficient mixed or decomposed batch again affects the quality of the frit negatively.
- Bulk Density It is the weight of granuled material which falls to each unit volume. It is not stable but can be arranged as ventilation and mechanic packaging by vibration.
- Real Density or Specific Weight The important subject here is weight difference particles and therefore, level of kinetic energy of single particle can reach. During mixture, fine particles which have high specific weight can move more easily than larger ones with a low specific weight and this affects homogenity of the mixture.
- Shape of Particle The particles broken irregularly with varying shapes exhibit their own characteristics.
- the fast firing cycle does not only identify the form but also identifies the amount of crystals which are regenerated.
- cooling rate does not modify the glass to be re-crystallized. Because the tiles over which glass ceramic glaze is applied are exposed to fast firing cycles, the devitrification kinetics and possible changes in the firing regime should always be taken into account. Therefore, important problems such as the colour shades and marks seen after firing the problems mentioned below in the industrial furnaces can be eliminated.
- frit application is important and, has been developed consistently.
- the purpose of fritting can be described as transforming suitable mixtures into glass by melting; a) Water soluble materials such as alkali carbonates, nitrides, borates etc. can not be used in glaze as they are dissolved in water. They are transformed into dissoluble form after fritting process. When a porous substrate is immersed into the glaze, first, it sustains the fused materials and the composition of the glaze changes. The coloring oxides being in frit disintegrate smoothly in the glaze and coloring power increases. b) Toxic compounds, especially lead compounds, become innocent when are fritted. c) They provide low firing temperature to glazes. d) They don’t affect the body chemically. Since they are applied as tiny layers, they provide a better fit to the body. e) A good homogenity is obtained especially in coloured glazes by frit application.
- percent of the composition of oxide are ranges of being given below:
- Component Amount ( wt %) R 2 O (Na 2 O, K 2 O) 1-5 RO(CaO, MgO, BaO) 10-40 R 2 O 3 (B 2 O 3 , Al 2 O 3 , Fe 2 O 3 *) 20-60 RO 2 (SiO 2 , ZrO 2 *) 10-50
- Resultant homogeneous mixtures are placed into either suitable ceramic, platinium, etc. crucibles.
- the appropriate temperature (1300-1500 °C) and time (30 minute – 3 hours) are set in related furnace.
- the melt is quenched into cold water providing quick-freezing while the furnace temperature is at appropriate high temperature.
- Frit is obtained as a result of melting of mentioned recipe at high tempertaure and quick-freezing in cold water.
- the wet product that is frit prepared according to the mentioned recipe and taken from water is subjected to grinding if it will be used for vetrosa applications after drying to obtain vetrosa frit appropriate size suitable for industrial application.
- the dry grinding of product being fritted of desired particle size range is between 38-250 ⁇ m for vetrosa applications.
- the frit is used as raw material fo glaze, a binder in abrasives, a melter in ceramic process such as decoration, a layer in electronic components, a glue in ceramic-metal and glass-metal pads.
- 90-95 % of the glaze being used in wall tiles manufacturing are frit based. The biggest factor is low firing temperature. They are ground in glaze mills by addition of sufficient amount of kaolin and pigments. Subsequently, the glaze prepared in mill is applied on biscuit. The fritted glaze is fired in single-fast-firing furnace for a shorter time as 35-40 minutes and a homogenous product is obtained.
- the transparent frits have usability with colouring oxides and phosphorescence pigments. In vetrosa applications, transparent frits having low melting temperatures and reduced particle size distributions are used.
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
Low temperature vetrosa decoration frit used with the phosphorescent pigments. This invention is about frits having low melting temperature. They can be used with phosphorescent pigments and evaluated in vetrosa decoration application of single-fast-fired glazed wall tiles. Their usage under industrial working condition do not cause any undesired consequences and supply decoration rich and functional new final products
Description
This invention is related with frits having low
melting temperature, which may be used with phosphorescent
pigments and evaluated in vetrosa decoration applications
of single-fast-fired glazed wall tiles, transparent, having
optimum properties for production method and obtained
product and having a wealth of usage.
The frit based glazes create a different group
with the usage advantage of fritted raw materials which are
soluble in water without fritting process and with
maturation characteristics over a wide temperature range.
The objectives of fritting are as follows;
An insoluble glass is formed by combining alkaline
carbonhydrates, nitrates, borates, etc. materials soluble in
water and melted with other raw materials to form frit. The
salts soluble within the slurry of glazes being generally
prepared with water are disadvantageous because of such a
dissolution, resulting a loss of some components which must
definetly remain in the system. Apart from this, the porous
biscuittends to absorb these salts and consequently, changes
the glaze composition in the dipping pool. The soluble salts
taken by the porous biscuit make the way to crystallisation
in corners during drying. These parts burn more intensely
and create problems in the glaze. Also, soluble salts cause
distortion of colours
- Slow reacting materials at low temperatures, as barium carbonates, strengthen the fludity when becoming frit components. Stronger fluidifiers increase the performance of fritting and improve the final appeal.
- In glaze preparation process, the fritting of raw materials being disadvantageous if used directly eliminates all the relevant undesired consequences.
- Frit is the major part of glaze stack. It takes up less space than the corresponding raw materials. Also, it is chemically less active because the decomposition and reaction of the thermal processes had been completed. Therefore, when frit is used the problems of coloring within and under glaze are minimized. The fritted glaze is applied in the form of a thinner layer and so, the product blends better to the spectrum.
- As the raw materials will show distinctness in the properties such as depthness, size, shape and hardness, they cause decomposition (segregation) in the batch. As fritting prevents such a tendency, it provides homogenity both in the batch and the end product. Apart from this, colours in the glaze are bright and more pleasant.
- Slow reacting materials at low temperatures, as barium carbonates, strengthen the fludity when becoming frit components. Stronger fluidifiers increase the performance of fritting and improve the final appeal.
- In glaze preparation process, the fritting of raw materials being disadvantageous if used directly eliminates all the relevant undesired consequences.
- Frit is the major part of glaze stack. It takes up less space than the corresponding raw materials. Also, it is chemically less active because the decomposition and reaction of the thermal processes had been completed. Therefore, when frit is used the problems of coloring within and under glaze are minimized. The fritted glaze is applied in the form of a thinner layer and so, the product blends better to the spectrum.
- As the raw materials will show distinctness in the properties such as depthness, size, shape and hardness, they cause decomposition (segregation) in the batch. As fritting prevents such a tendency, it provides homogenity both in the batch and the end product. Apart from this, colours in the glaze are bright and more pleasant.
If lead bearing compounds available in glaze
treshing, the glaze slurry must be mixed very well before
and during the application, otherwise, heavy compounds may
precipitate under suitable conditions. Due to pre-melting,
large pores which may remain in the glaze and release
bubbles are eliminated. On the other hand, being of some raw
clay in the fritted glaze batch may overcome some problems
like fine sized bubbles.
Two of the most important reasons for using frit
are to eliminate the water soluble raw materials access in
to the glaze batch and to avoid the possible harm coming
from toxic raw materials.
Solubility: All substantially water soluble raw
materials must be fritted. These are alkaline salts such as
sodium carbonate, potassium nitrate and chloride and common
compounds such as lithium oxide, boric acid, and alkaline
borade. All of them are strong fluxes and have considerable
effects over the physical characteristics of glaze. Calcium
carbonate has solubility in water also magnesium oxide and
magnesium carbonate are much more soluble in water.
Solubility of Alkali Silicates: As the compunds of
alkali and silica are soluble, earth alkaline such as
calcium, magnesium, strontium and barium are contributed to
the frit harmony in addition to alkali. Lead oxide and zinc
alone or with earth alkali compounds stay together for the
same reason.
Aluminium Oxide: It is used in alkali not
exceeding0.1 or 0.2 moles because it has increasing property
of the thermal strength and viscosity at higher rates.
The Ratio of Alkali to Other RO Elements: To keep
the water solubility of the end product at a lower level,
the total molecular alkali amount in frit may not be more
than 50 % of the total RO. Otherwise, some other insoluble
alkali such as feldspar might be necessery to join the RO.
Acidic Components in Frit: Practically silica is
an essential acidic element in frit generally, with the
presence of boric oxide. Apart from this, there are also
some other suitable oxides in the system. Silica provides
insolubility but to prepare a melt with acceptable fludity
at low melting temperature, molecular equivalent should not
be under the rate of 1:1.5 and not be over the rate of 1:3.
Presence of boric acid increases melting ability and
fluidity considerably. To keep solubility at low level, the
rate of boric acid should not be more than the rate of the
silica by 1:2.
Frit Production and Parameters Affecting The Production
Some ceramic manufacturers produce frit themselves
which they consume in large quantities, they also buy
special kinds of frits they used in lesser amount from frit
producers. The raw materials used in the production are
provided directly from the market to be used according to
the recipe. The flow chart of frit production is given in
Figure 2.1. Such a production can be seen as a simple
melting process however, there are many parameters which
affect this production. If the subjects such as furnace
design, refractory, heat transfer and melt chemistry are not
understood well, decrease in the melting performance of the
furnace might be observed. Weighing is the most basic and
important procedure in frit production process. Stored raw
materials are feed into weighing silo by a conveyor system
and this procedure continues until desired amounts of each
raw material are taken. In some cases, raw materials added
is taken directly from their bags by weighing. The relevant
processes are better performed by computerized systems
because it is less likely to make mistakes. All the raw
materials should be stored in to silos. After weighing the
batch, they are throughly mixed and charged into the frit furnace.
Mixing procedure consists of two stages. First and
basic of these process is mixing the batch when it is dry
and second is to mix it in the furnace. Dry mixing before
fritting might seem to be easy at first but different
characters of batch components do not usually allow such
easiness. Raw materials used in fritting indicate
distinctness in size distribution, density, particle shape
and surface characteristics and accordingly it is hard to
obtain homogeneity.
A completed mixture must consist of all the
components at direct proportion. An insufficient mixing time
and excesive loading decrease the quality of the mixture.
Insufficient mixed or decomposed batch again affects the
quality of the frit negatively.
The changes which might occur in the particle
shape and size ditribution, density and surface
characteristics of the raw materials used in the frit
batchmay lead difficulties to get a homogeneous mixture.
Therefore, mentioned characteristics should be well
understood and must be preciously controlled.
Division of Shape and Size: It is the most
important factor in mixture. As particles are completed in a
specific geometric shapes which is approximately
dimensional, after milling and grinding they have a wide
shape and varying size. If two elements are different in
particle size from each other, their segregation are unavoidable.
Bulk Density: It is the weight of granuled
material which falls to each unit volume. It is not stable
but can be arranged as ventilation and mechanic packaging by vibration.
Real Density or Specific Weight: The important
subject here is weight difference particles and therefore,
level of kinetic energy of single particle can reach. During
mixture, fine particles which have high specific weight can
move more easily than larger ones with a low specific weight
and this affects homogenity of the mixture.
Shape of Particle: The particles broken
irregularly with varying shapes exhibit their own characteristics.
Surface Characteristics: They are about the
surface area. Fine particles are prone to clumping
(agglomeration). The other components may hold electrostatic
charge and some particles can be in the granular form. These
characteristics limit the achievement of smooth and
homogeneous mixture.
The fast firing cycle does not only identify the
form but also identifies the amount of crystals which are
regenerated. When the firing regime has reached to the point
of maximum firing heat that is under the melting heat of
crystal phase, cooling rate does not modify the glass to be
re-crystallized. Because the tiles over which glass ceramic
glaze is applied are exposed to fast firing cycles, the
devitrification kinetics and possible changes in the firing
regime should always be taken into account. Therefore,
important problems such as the colour shades and marks seen
after firing the problems mentioned below in the industrial
furnaces can be eliminated.
Technical problems of the invention aims to solve:
In ceramic tile industry, there are different
kinds of low melting transparent frits. But each frit with
different thermal expansion coefficient value has limited
use for both vetrosa and 3rd firing (decor)
applications, and most of them are not suitable for the
evaluation of phosphorescent pigments. The aim is to
develop new recipes and systems to produce transparent
vetrosa frit having low melting temperature, thermal
expansion coefficient and, is very suitable for the usage of
phosphorescent pigments.
In ceramic technology, frit application is
important and, has been developed consistently. The purpose
of fritting can be described as transforming suitable
mixtures into glass by melting;
a) Water soluble materials such as alkali carbonates, nitrides, borates etc. can not be used in glaze as they are dissolved in water. They are transformed into dissoluble form after fritting process. When a porous substrate is immersed into the glaze, first, it sustains the fused materials and the composition of the glaze changes. The coloring oxides being in frit disintegrate smoothly in the glaze and coloring power increases.
b) Toxic compounds, especially lead compounds, become innocent when are fritted.
c) They provide low firing temperature to glazes.
d) They don’t affect the body chemically. Since they are applied as tiny layers, they provide a better fit to the body.
e) A good homogenity is obtained especially in coloured glazes by frit application.
a) Water soluble materials such as alkali carbonates, nitrides, borates etc. can not be used in glaze as they are dissolved in water. They are transformed into dissoluble form after fritting process. When a porous substrate is immersed into the glaze, first, it sustains the fused materials and the composition of the glaze changes. The coloring oxides being in frit disintegrate smoothly in the glaze and coloring power increases.
b) Toxic compounds, especially lead compounds, become innocent when are fritted.
c) They provide low firing temperature to glazes.
d) They don’t affect the body chemically. Since they are applied as tiny layers, they provide a better fit to the body.
e) A good homogenity is obtained especially in coloured glazes by frit application.
They provide 100-150 oC reduction
depending on the glaze composition when compared to the raw
glazes in the same composition, so the spent energy for
fritting may be acquired during firing. Changing of firing
ranges of frit glazes leads to elimination of lots of firing
defects. As the glaze composition being fritted has
homogeneous structure,they are more reliable in operation.
It is known that the fritting time, the particle size of the
raw materials affect the fritting process.
Description of the invention:
A low temperature frit having appropriateexpansion
coefficient, compatible with phosphorescence pigments,
transparent, that can be used as vetrosa frit in decor
applications. When we characterize in terms of composition
details, the percent of the composition of oxide are ranges
of being given below:
| Component Amount ( wt %) |
| R 2 O (Na 2 O, K 2 O) 1-5 RO(CaO, MgO, BaO) 10-40 R 2 O 3 (B 2 O 3 , Al 2 O 3 , Fe 2 O 3 *) 20-60 RO 2 (SiO 2 , ZrO 2 *) 10-50 |
*: Comes from the raw materials as impurity and
its quantities can be ignored.
Production Method:
- In the mentioned recipe zinc oxide (ZnO), lithium carbonate (Li2CO3) boric acid (H3BO3), potassium feldspar or potassium nitrate (KNO3), barium carbonate (BaCO3) or wollastonite, quartz, alumina (Al2O3), sodium carbonate (Na2CO3) or sodium feldspar are used supplying relevant oxides.
- Chemical analysis of the starting raw materials are determined in details by x-ray fluorescence (XRF) analysis.
- The Seger calculations are made according to the chemical analysis results of the raw materials mentioned in the recipe.
- Homogeneous mixtures are prepared for the mentioned recipe.
- Resultant homogeneous mixtures are placed into either suitable ceramic, platinium, etc. crucibles.
- To get glass melting at high temperature from batches being prepared according to mentioned recipe and loaded crucibles, the appropriate temperature (1300-1500 °C) and time (30 minute – 3 hours) are set in related furnace.
- To get glass melting, glass melting furnace or a furnace that can reach required temperatures and appropriate for pouring of melt.
- After the mentioned recipe is melt at appropriate temperature and being kept wait appropriate time, the melt is quenched into cold water providing quick-freezing while the furnace temperature is at appropriate high temperature.
- Frit is obtained as a result of melting of mentioned recipe at high tempertaure and quick-freezing in cold water.
- The wet product that is frit prepared according to the mentioned recipe and taken from water is subjected to grinding if it will be used for vetrosa applications after drying to obtain vetrosa frit appropriate size suitable for industrial application.
- In the mentioned recipe, the dry grinding of product being fritted of desired particle size range is between 38-250 μm for vetrosa applications.
- In the mentioned recipe zinc oxide (ZnO), lithium carbonate (Li2CO3) boric acid (H3BO3), potassium feldspar or potassium nitrate (KNO3), barium carbonate (BaCO3) or wollastonite, quartz, alumina (Al2O3), sodium carbonate (Na2CO3) or sodium feldspar are used supplying relevant oxides.
- Chemical analysis of the starting raw materials are determined in details by x-ray fluorescence (XRF) analysis.
- The Seger calculations are made according to the chemical analysis results of the raw materials mentioned in the recipe.
- Homogeneous mixtures are prepared for the mentioned recipe.
- Resultant homogeneous mixtures are placed into either suitable ceramic, platinium, etc. crucibles.
- To get glass melting at high temperature from batches being prepared according to mentioned recipe and loaded crucibles, the appropriate temperature (1300-1500 °C) and time (30 minute – 3 hours) are set in related furnace.
- To get glass melting, glass melting furnace or a furnace that can reach required temperatures and appropriate for pouring of melt.
- After the mentioned recipe is melt at appropriate temperature and being kept wait appropriate time, the melt is quenched into cold water providing quick-freezing while the furnace temperature is at appropriate high temperature.
- Frit is obtained as a result of melting of mentioned recipe at high tempertaure and quick-freezing in cold water.
- The wet product that is frit prepared according to the mentioned recipe and taken from water is subjected to grinding if it will be used for vetrosa applications after drying to obtain vetrosa frit appropriate size suitable for industrial application.
- In the mentioned recipe, the dry grinding of product being fritted of desired particle size range is between 38-250 μm for vetrosa applications.
Applying the invention to industry:
The frit is used as raw material fo glaze, a
binder in abrasives, a melter in ceramic process such as
decoration, a layer in electronic components, a glue in
ceramic-metal and glass-metal pads.
Frits being mostly common in wall and floor tiles
industry bring advantages along as obtaining homogeneous
glaze, lowering glaze ripening the high temperature and
quicken the chemical reactions. 90-95 % of the glaze being
used in wall tiles manufacturing are frit based. The biggest
factor is low firing temperature. They are ground in glaze
mills by addition of sufficient amount of kaolin and
pigments. Subsequently, the glaze prepared in mill is
applied on biscuit. The fritted glaze is fired in
single-fast-firing furnace for a shorter time as 35-40
minutes and a homogenous product is obtained. Especially the
transparent frits have usability with colouring oxides and
phosphorescence pigments. In vetrosa applications,
transparent frits having low melting temperatures and
reduced particle size distributions are used.
Claims (2)
- Transparent vetrosa frit used with the phosphorescent pigments melts at low temperature. Its chemical composition is presented below: Reference---Table 1.
- The details about the production method of transparent vetrosa frit are given as follows:
- In the mentioned recipe zinc oxide (ZnO), lithium carbonate (Li2CO3) boric acid (H3BO3), potassium feldspar or potassium nitrate (KNO3), barium carbonate (BaCO3) or wollastonite, quartz, alumina (Al2O3), sodium carbonate (Na2CO3) or sodium feldspar are used supplying relevant oxides.
- Chemical analysis of the starting raw materials were determined in details by x-ray fluorescence analysis (XRF).
- The Seger calculations were made according to the XRF results of the raw materials mentioned in the recipe.
- Homogenous mixtures were prepared for the mentioned recipe.
- Resultant homogenous mixtures were placed into either suitable ceramic or platinium crucibles.
- For glass melting loaded crucibles were placed into an electrically heated, bottom loaded furnace and heated up to 1300-1500 oC with 30 minutes- 3 hours holding time at mentioned temperatures.
- After being sure of the fact that the homogeneous glass was obtained at the relevant melting temperature, the melt is quenched into cold water providing quick-freezing.
- Frit is obtained as a result of such a process mentioned water.
- Frits were subjected to grinding after drying to obtain appropriate size suitable for vetrosa decor application of single-fast-fired glazed ceramic wall tiles.
- For vetrosa decoration applications desired particle size range falls between 38-250 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/TR2015/050007 WO2016200351A1 (en) | 2015-06-10 | 2015-06-10 | The transparent vetrosa frit which melts at low temperatures having usability with phosphorescence pigments |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/TR2015/050007 WO2016200351A1 (en) | 2015-06-10 | 2015-06-10 | The transparent vetrosa frit which melts at low temperatures having usability with phosphorescence pigments |
Publications (1)
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|---|---|
| WO2016200351A1 true WO2016200351A1 (en) | 2016-12-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017144745A1 (en) * | 2016-02-26 | 2017-08-31 | Celso Rodriguez Barreiro | Sealing compound |
| CN110563335A (en) * | 2019-09-10 | 2019-12-13 | 中南大学 | lead-free transparent fritted glaze and preparation method thereof |
| CN113896518A (en) * | 2021-10-14 | 2022-01-07 | 广东欧文莱陶瓷有限公司 | Color-changeable rock plate and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2573200A (en) * | 1949-06-29 | 1951-10-30 | Westinghouse Electric Corp | Glass for embedding zinc sulfide phosphors |
| SU1592292A1 (en) * | 1988-06-15 | 1990-09-15 | Gnii Stroitelnoj Keramiki | Green glaze |
| US5677250A (en) * | 1994-10-17 | 1997-10-14 | Cooper Industries, Inc. | Low-temperature lead-free glaze for alumina ceramics |
| US20050179008A1 (en) * | 2004-02-18 | 2005-08-18 | Zhiguo Xiao | Light-storage self-luminescent glass and the process for producing the same |
| US20060214134A1 (en) * | 2003-04-01 | 2006-09-28 | Noriaki Masuda | Luminescent glass article and method of manufacturing the same |
| JP2007302858A (en) * | 2006-04-11 | 2007-11-22 | Nippon Electric Glass Co Ltd | Luminescent color-shifting material and luminescent color-shifting member |
-
2015
- 2015-06-10 WO PCT/TR2015/050007 patent/WO2016200351A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2573200A (en) * | 1949-06-29 | 1951-10-30 | Westinghouse Electric Corp | Glass for embedding zinc sulfide phosphors |
| SU1592292A1 (en) * | 1988-06-15 | 1990-09-15 | Gnii Stroitelnoj Keramiki | Green glaze |
| US5677250A (en) * | 1994-10-17 | 1997-10-14 | Cooper Industries, Inc. | Low-temperature lead-free glaze for alumina ceramics |
| US20060214134A1 (en) * | 2003-04-01 | 2006-09-28 | Noriaki Masuda | Luminescent glass article and method of manufacturing the same |
| US20050179008A1 (en) * | 2004-02-18 | 2005-08-18 | Zhiguo Xiao | Light-storage self-luminescent glass and the process for producing the same |
| JP2007302858A (en) * | 2006-04-11 | 2007-11-22 | Nippon Electric Glass Co Ltd | Luminescent color-shifting material and luminescent color-shifting member |
Non-Patent Citations (5)
| Title |
|---|
| A. TUNALI ET AL: "Influence of the Photoluminescent Pigments' Particle Size Distribution on the After Glow Duration", ACTA PHYSICA POLONICA: SERIES A, vol. 125, no. 2, 1 January 2014 (2014-01-01), PL, pages 513 - 514, XP055240445, ISSN: 0587-4246, DOI: 10.12693/APhysPolA.125.513 * |
| DATABASE WPI 15 September 1990 Derwent World Patents Index; AN 1991-139548, XP002753363, KVYATKOVSKAYA KLARA K [SU]; RUSS NATATYA M [SU]; KOSORUKOVA ELENA S [SU]: "Glaze for coloured ceramics tiles - contains oxide(s) of silicon, aluminium, iron, boron, chromium, calcium, copper, sodium, potassium, titanium and additional barium" * |
| KAYA SELVIN YESILAY ET AL: "Process parameters determination of phosphorescent pigment added, frit-based wall tiles vetrosa decorations", CERAMICS INTERNATIONAL, vol. 38, no. 4, 1 January 2011 (2011-01-01), pages 2757 - 2766, XP028904582, ISSN: 0272-8842, DOI: 10.1016/J.CERAMINT.2011.11.045 * |
| PEKKAN K ET AL: "Zircon-free frits suitable for single fast-firing opaque wall tile glazes and their industrial productions", JOURNAL OF THE EUROPEAN CERAMIC SOCIETY, ELSEVIER SCIENCE PUBLISHERS, BARKING, ESSEX, GB, vol. 29, no. 9, 1 June 2009 (2009-06-01), pages 1571 - 1578, XP026053030, ISSN: 0955-2219, [retrieved on 20090104], DOI: 10.1016/J.JEURCERAMSOC.2008.10.010 * |
| WALTER KERSTAN: "Keramische Glasuren - Aufbau, Farbgebung, Dekortechniken und Rohstoffe", SPRECHSAAL,, vol. 120, no. 4, 1 April 1987 (1987-04-01), pages 308 - 312, XP001269056 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017144745A1 (en) * | 2016-02-26 | 2017-08-31 | Celso Rodriguez Barreiro | Sealing compound |
| CN110563335A (en) * | 2019-09-10 | 2019-12-13 | 中南大学 | lead-free transparent fritted glaze and preparation method thereof |
| CN110563335B (en) * | 2019-09-10 | 2021-12-21 | 中南大学 | Lead-free transparent fritted glaze and preparation method thereof |
| CN113896518A (en) * | 2021-10-14 | 2022-01-07 | 广东欧文莱陶瓷有限公司 | Color-changeable rock plate and preparation method thereof |
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