US 20130017388A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2013/0017388 A1
(43) Pub. Date:
BOGUSLAVSKY et al.
(54)
COMPOSITIONS PROVIDING FROST
(52)
APPEARANCE FOR PRINTING ON GLASS
OR CERAMIC SUBSTRATES AND METHODS
FOR THE USE THEREOF
(57)
(76) Inventors: Lior BOGUSLAVSKY, Petah-Tikva
(IL); Ariel LITWAK, Ramat-Ha’Sharon
(IL); Michael KHEYFETS, Jerusalem
(IL)
Jan. 17, 2013
US. Cl. ..................... .. 428/312.6; 106/287.1; 65/22
ABSTRACT
A method of producing a substrate having a frosted appear
ance, an article having a frosted appearance and frost-impart
ing compositions are disclosed. The method includes apply
(21) Appl.N0.: 13/547,543
ing a frost-imparting composition onto a ceramic substrate
and ?ring the coated substrate above 4000 C. to impart the
(22) Filed:
frost appearance. The frost-imparting composition comprises
a liquid vehicle, 20% to 90% by Weight of glass frit particles
Jul. 12, 2012
Related US. Application Data
(60)
Provisional application No. 61/507,622, ?led on Jul.
14, 2011.
and less than 10% by Weight of at least one gas-releasing
material, inactive beloW an activation temperature of at least
4000 C. The gas releasing material may include carbonate,
nitrate, iodate, bromate, chlorate, ?uoride, manganate,
Publication Classi?cation
(51)
Int. Cl.
C09D 5/00
B32B 17/00
C03C 17/04
dimanganate and sulfate compounds. The ?ring temperature
is chosen to be above the activation temperature of the gas
(2006.01)
(2006.01)
(2006.01)
releasing material, above Which the gas-releasing material
yields gas bubbles and above a temperature that causes the
glass frit particles to behave as a viscous liquid.
US 2013/0017388 A1
Jan. 17, 2013
COMPOSITIONS PROVIDING FROST
APPEARANCE FOR PRINTING ON GLASS
OR CERAMIC SUBSTRATES AND METHODS
FOR THE USE THEREOF
printing processes used for glass and ceramic printing rely on
CROSS REFERENCE TO RELATED
APPLICATIONS
oxides and salts) and ?nely ground glass particles, called frit.
[0001] This application claims bene?t of US. Provisional
Application No. 61/507,622 ?led on Jul. 14, 2012, entitled,
“COMPOSITIONS PROVIDING FROST APPEARANCE
FOR PRINTING ON GLASS OR CERAMIC SUB
STRATES AND METHODS FOR THE USE THEREOF”,
Which is hereby incorporated by reference.
BACKGROUND
a variety of paste and ink systems. Some of these inks are
inorganic.
[0010] Ceramic colors, as inorganic ceramic inks are
knoWn, are a mixture of mineral-based pigments (metal
These materials are fused to the ceramic substrate surface on
Which they are coated or printed by calcining (“?ring”) them
at temperatures betWeen 500-1450o C. Firing temperatures
vary depending on the make-up of the color, the nature of
substrate, and other application criteria. While these inks are
typically called “inorganic”, they may also contain small
amounts of organic material. The organic components are the
materials in Which the pigment and frit are suspended to
create a printing ink. These organic materials are expected to
burn out during ?ring Without affecting print quality and ?nal
[0002] Ceramic materials are hard, brittle, heat-resistant
and corrosion-resistant substrates made by shaping and then
color.
[0011]
heating a non-metallic mineral, such as clay, at a high tem
printing, ?exographic printing, gravure printing, roller coat
ing, dip coating, curtain coating, air brushing, or other coat
ing, spraying and analog printing techniques are (or can be)
perature. Enamels, porcelain, bricks, and glasses are
examples of materials that are produced by molding or shap
ing minerals and baking or ?ring them at high temperatures.
[0003] Glass is a hard, brittle and often transparent solid
that is used, for example, in the construction of WindoWs,
bottles and lenses. Many types of glass contain silica as their
main component. Common types of glass include, inter-alia,
soda-lime glass, borosilicate glass, boron and/or phospho
rous doped glass, silicon dioxide, silicon nitride, and alumi
In some cases, screen printing, pad printing, offset
used to imitate a frost appearance on glass. These techniques
require the preparing of plates, cylinders, masks or screens as
a master copy, Which must be maintained and stored, and then
used to print the image on the glass or the ceramic substrate
over and over again. The frost appearance in these coating and
printing techniques can be achieved by using frost-imparting
ink or pastes containing a combination of glass frits, in Which
num oxynitride.
a high melting frit is included, and/or ceramic (or inorganic)
[0004]
particles having an average particle siZe above several
micron. Such ink paste products are also highly viscous, since
In general, frosted glasses has the effect of rendering
the glass translucent by scattering of light during transmis
sion, thus blurring images vieW While still transmitting light.
[0005] Providing a non-colored pattern to glass or ceramic
substrates may be used for example, in architecture, to give
rough, opaque or “matt” patterns or may be used, for
example, in surfaces on WindoWs or glass doors both for
aesthetic purposes and for avoiding accidental collisions.
[0006]
A frost appearance of glass has traditionally been
performed by physical (mechanical) or chemical etching pro
cesses.
[0007] In the physical process ?ne particles of sand are
blasted against an unprotected portion of the surface to be
decorated according to a mask. The sandblasting erodes the
unmasked portion of the glass surface to produce a frosted
they contain high concentration of the particles. After ?ring,
a frosted appearance is produced by the high melting frits
and/or the ceramic (or inorganic) particles remaining on the
surface.
SUMMARY OF THE INVENTION
[0012]
Embodiments of the inventions are directed to a
method of producing a substrate having a frosted appearance,
an article having a frosted appearance and frost-imparting
appearance that provides a contrast for the untouched smooth
compositions. The method includes applying a frost-impart
ing composition onto a ceramic substrate and ?ring the coated
substrate above 4000 C., usually in the range between 4000 C.
and 750° C. to impart the frost appearance. The frost-impart
ing composition may comprises a liquid vehicle, 20% to 90%
transparent part of the glass. This process is tedious and
by Weight of glass frit particles and less than about 10% by
costly.
[0008]
Chemical etching comprises dipping or coating a
glass or mask-covered glass in or With an etching composition
containing strong acids such as hydro?uoric acid, nitric acid,
hydrochloric acid, and sulfuric acid, creating a desired etched
pattern. HoWever, the strong acids used in conventional
chemical etching processes cause a number of serious prob
lems. Namely, during the etching step, poisonous gases,
Weight of at least one gas releasing material, inactive beloW an
activation temperature of at least 4000 C. The gas releasing
material may be any suitable material, as described herein,
including for example carbonates, nitrates, iodates, bromates,
clorates, ?uorides, manganates, dimanganates and sulfates.
The ?ring temperature is chosen to be above the activation
temperature of the gas releasing material, above Which the gas
releasing material yields gas bubbles and above a temperature
Which are harmful to humans, are generated. Also, the Waste
Water produced during such processes needs to be treated in a
that causes the glass frit particles to behave as a viscous
safe manner so as not to raise environmental pollution,
[0013] The frost-imparting compositions may be suitable
for inkjet printing, screen printing, pad printing, offset print
ing, ?exographic printing, gravure printing, roller coating,
dip coating, curtain coating and spraying. According to
embodiments of the invention, the frost-imparting composi
including Water pollution, air pollution and the like. Due to
these problems, chemical etching has not been Widely prac
ticed in Well developed nations on an industrial scale and thus,
cannot ful?ll increasing demands for frosted glass.
[0009] Several methods are available for decorating glass
and ceramics With high-quality images. The coating and
liquid.
tion is an ink jet composition, Which is dispensed from an
inkjet system.
US 2013/0017388 A1
[0014]
Jan. 17, 2013
The frosted ?red article according to embodiments
[0018]
imparting coating composition. Prior to ?ring, the frost-im
parting composition comprises a liquid vehicle, 20% to 90%
by Weight of glass frit particles and less than 10% by Weight
a liquid vehicle and at least one gas-forming material or
gas-releasing material, Which releases carbon dioxide (CO2),
and/or Water (H2O), and/or nitrogen oxides (NO and/ or NOZ),
and/or oxygen (O2), and/or nitrogen (N2), and/or sulfur diox
ide (SOZ), and/or iodine (I2) and/or bromine (Br2), and/or
of at least one gas releasing material, inactive beloW an acti
vation temperature of at least 4000 C., the gas releasing mate
rial comprised of carbonate, bicarbonate, nitrate, nitrite,
iodate, periodate, bromate, perbromate, clorate, perchlorate,
?uoride, manganate, dimanganate, permanganate, hypoman
ganate, chromate, dichromate, sulfate, sul?te, dithionite,
thiosulfate, cyanate, thiocyanate compound or any combina
tion thereof. After being ?red at a ?ring temperature of above
4000 C., Wherein after being ?red at a ?ring temperature of
above 4000 C., areas of the substrate that are exposed to the
coating composition exhibits a frosted appearance, Wherein
the temperature is chosen to be above the activation tempera
ture of the gas releasing material, above Which the gas releas
ing material yields gas bubbles and above a temperature that
causes the glass frit particles to behave as a viscous liquid.
DETAILED DESCRIPTION OF EMBODIMENTS
[0015]
In some embodiments of the invention, a frost-im
parting composition Which may be in the form of an ink,
slurry, suspension or a paste may include glass frit particles;
of the invention comprises ceramic substrate and a frost
chlorine (C12), and/or ?uorine (F2), and/ or carbon monoxide
(CO), and various combination thereof folloWing decompo
sition or reaction With other materials. The terms “gas-form
ing material” and “gas-releasing material” are used inhere
interchangeably. The composition may further include a ?xa
tion agent comprising an organic component. In some
embodiments the frost imparting composition may include a
pigment.
[0019]
The gas-forming material/ s is/are inactive When
kept at storage and during the printing or coating stages and
While kept beloW their activation temperature. The term
“inactive” With respect to the gas-forming materials refers to
the stage prior to decomposition or undergoing reaction that
yields gas bubbles. These materials decompose or react upon
?ring above their activation temperature, Which is above 4000
In the folloWing detailed description, numerous spe
C. to release one or more of the above mentioned gases.
ci?c details are set forth in order to provide a thorough under
standing of the invention. HoWever, it Will be understood by
[0020] In some embodiments of the invention, the frost
imparting composition includes at least one gas-releasing
those skilled in the art that the present invention may be
material in a form of micron and/ or sub-micron particles. The
practiced Without these speci?c details. In other instances,
Well-knoWn methods, procedures, and components have not
been described in detail so as not to obscure the present
invention.
[0016] Embodiments of the invention relate to a method for
gas releasing material may include carbonate, bicarbonate,
nitrate, nitrite, iodate, periodate, bromate, perbromate, clor
ate, perchlorate, ?uoride, manganate, dimanganate, perman
ganate, hypomanganate, chromate, dichromate, sulfate,
sul?te, dithionite, thiosulfate, cyanate, thiocyanate com
imparting a frosted appearance to a ceramic substrate or
pound or any combination thereof
[0021] In some embodiments of the invention, the gas
ceramic articles using a frost-imparting composition in liq
uid, slurry, suspension or paste form, frosting-imparting
releasing material solubility in the composition is less than
20%. In other embodiments of the invention, the gas-releas
methods, printing processes, articles of manufacture com
prising the frost-imparting composition and glass or ceramic
substrates having a frost effect that is formed by using the ink,
paste, suspension or paste frost-imparting composition and
the methods described herein.
[0017] The frost appearance is obtained by proper selection
of the composition, selected to suit the relevant application
ing material is an alkaline compound. In other embodiments
of the invention, the gas-forming material is an alkaline earth
metal compound. In other embodiments of the invention, the
gas-forming material is a transition metal compound. In some
embodiments of the invention, the gas-forming material is a
process such as printing or coating. The exact frost appear
ance can be controlled by the printing mode of the printer and
the exact conditions of the ?ring process.
post-transition metal compound.
[0022] Tables 1-10 provide non-exhaustive lists of exem
plary compounds that may be used as a gas-releasing material
in connection With embodiment of the invention.
TABLE 1
Carbonate salts and minerals releasing carbon dioxide CO2 during thermal decomposition
Chemical name
Other names
Calcium carbonate
Limestone, calcite,
aragonite, chalk,
Chemical
formula
(empirical)
CaCO3
marble, Vaterite,
Travertine, Tufa,
Glendonite, Nicols,
Related compounds
CaCO3°H2O (Hydrated Calcium Carbonate;
Monohydrocalcite), CaCO3°6H2O (Ikaite), shells of
marine organisms, snails, pearls, eggshells,
agricultural lime
Manganocalcite —
variety, Glendonite —
pseudomorph
Magnesium carbonate
Magnesite, Bitter
spar, Hoshiite
MgCO3
MgCO3°H2O (magnesium carbonate monohydrate),
MgCO3°2H2O (magnesium carbonate dehydrate;
Barringtonite), MgCO3°3H2O (magnesium carbonate
trihydrate; Nesequehonite), MgCO3°5H2O
(magnesium carbonate pentahydrate; Lansfordite),
Mg2CO3(OH)2°3H2O (Hydrated magnesium
US 2013/0017388 A1
Jan. 17, 2013
TABLE l-continued
Carbonate salts and minerals (releasing carbon dioxide (CO7) during thermal decomposition)
Chemical name
Other names
Chemical
formula
(empirical)
Related compounds
carbonate hydroxide; artinite),
4MgCO3°Mg(OH)2°5H2O (dypingite),
Mg5(CO3)4(OH)2°4H2O (Hydromagnesite)
Strontium carbonate
Barium carbonate
Strontianite
Witherite
SrCO3
BaCO3
Sodium carbonate
Washing soda, Soda
ash, Soda crystals,
Sal Soda, Natrite
Na2CO3
Na2CO3°H2O (sodium carbonate monohydrate),
Na2CO3°1OH2O (sodium carbonate decahydrate;
Natron), Na2(CO3)°H2O (Hydrated sodium
carbonate; Thermonatrite), Na3(HCO3)(CO3)°2H2O
(Hydrated sodium Bicarbonate Carbonate; Trona),
Na5(CO3)(HCO3)3 (Sodium carbonate bicarbonate;
Wegscheiderite)
Potassium carbonate
Lithium carbonate
Potash, pearl ash
Dilithium carbonate,
Carbolith, Cibalith
KZCO3
Li2CO3
S, Duralith, Eskalith,
Lithane, LithiZine,
Lithobid, Lithonate,
Lithotabs Priadel,
Zabuyelite
Rubidium carbonate
Cesium carbonate
Caesium carbonate
Rb2CO3
Cs2CO3
Beryllium carbonate
Manganese carbonate
Rhodochrosite,
BeCO3
MnCO3
Iron carbonate
Manganese spar
Siderite, Chalybite,
BeCO3°4H2O, (BeO5)°CO2°5H2O
Dialogite,
FeCO3
Iron spar, Spathose
iron
Cadmium carbonate
Otavite
CdCO3
Zinc carbonate
Smithsonite, Zinc
spar, Calamine,
ZnCO3
Zn5(CO3)2(OH)6 (Zinc carbonate hydroxide;
HydroZincite; Zinc bloom)
Copper carbonate
Cupric carbonate
CuCO3
Cu3(OH)2(CO3)2 (Copper carbonate hydroxide;
aZurite), Cu2(OH)2CO3 (Copper carbonate
Nickel carbonate
Nickelous carbonate
NiCO3
Ni4CO3(OH)6(H2O)4 (basic nickel carbonate),
Galmei
hydroxide; malachite)
NiCO3°6H2O (Nickel carbonate hexahydrate;
Hellyerite), Ni2(CO3)(OH)2 (Nickel carbonate
hydroxide; Nullaginite)
Cobalt carbonate
Cobaltous
CoCO3
carbonate,
CoCO3(Co(OH)X(H2O)y (basic cobalt carbonate),
other cobalt carbonate hydroxides
Spherocobaltite,
Sphaerocobaltite
Silver carbonate
Lead carbonate
Ag2CO3
Cerussite
PbCO3
2PbCO3°Pb(OH)2 (White lead), PbCO3°PbO (Lead
carbonate oxide; Shannonite),
3PbCO3°Pb(OH)2°PbO, PbCO3°2PbO,
Pb3(CO3)2(OH)2 (Lead carbonate hydroxide;
Hydrocerussite), Pb1O(CO3)6O(OH)6, (Lead
Aluminum carbonate
Thallium carbonate
Thallium
A12 (CO3)3
Tl2CO3
carbonate oxide hydroxide; Plumbonacrite)
Strontiodesserite
monocarbonate
Lanthanum carbonate
Uranium carbonate
La2(CO3)3
UOZCO3
La2(CO3)3 °8H2O
UO2CO3°H2O, (Blatonite)
Yttrium carbonate
Y2 (CO3)3
Y2(CO3)3°xH2O (Yttrium carbonate hydrate)
Chromium carbonate
Cerium carbonate
Thorium carbonate
Cr2(CO3)3
Ce2(CO3)3
Th(CO3)2
Ce2(CO3)3°5H2O
Praseodymium carbonate
Bismuth Carbonate
Pr2 (CO3)3
Bi2(CO3)3
Pr2(CO3)3 °8H2O
(BiO)2CO3 (Bismuth carbonate, basic; Bismuth
Uranyl carbonate,
Rutherfordine
Subcarbonate) , (BiO)2CO3 °5H2O
US 2013/0017388 A1
[0023] More carbonate minerals that can be used according
to some embodiments of the invention are CaMg(CO3)2 (Cal
cium magnesium carbonate; Dolomite), (Ni,Fe,Mg)CO3
(Nickel magnesium iron carbonate; Gaspeite), Ca(Mn,Mg,
Fe)(CO3)2 (Calcium manganese magnesium iron carbonate;
Ankerite; Kutnohorite; Kutnahorite; KuZmenkoite), CaZn
(CO3)2 (Calcium Zinc carbonate; Minrecordite), BaCa(CO3)2
(Barium calcium carbonate; Barytocite; Alstonite; Bromlite;
Paralstonite; Barytocalcite), (Cu,Zn)2CO3(OH)2 (Copper
Zinc carbonate hydroxide; Rosasite), (Zn,Cu)5(CO3)2(OH)6
(Zinc copper carbonate hydroxide; Aurichalcite), Pb2Cl2CO3
(Lead carbonate chloride; Phosgenite), (Ce,La,Y)CO3F (Ce
Jan. 17,2013
(CO3)(OH)2.0.5H2O (Hydrated magnesium carbonate
hydroxide; Pokrovskite), Mg6Fe2(CO3)(OH)l6.4H2O (Hy
drated magnesium iron carbonate hydroxide; Pyroaurite),
Mg4Al2(OH)12CO3.4H2O (Hydrated magnesium aluminum
carbonate hydroxide; Quintinite), (Cu,Ni)2(CO3)(OH)2
(Copper nickel carbonate hydroxide; Glaukosphaerite; Glau
kospherite), (Cu,Co)2CO3(OH)2 (Copper cobalt carbonate
hydroxide; KolWeZite), (Mg,Cu)2(CO3)(OH)2 (Magnesium
copper carbonate hydroxide; Mcguinnessite), (Zn,Cu)2(CO3)
(OH)2 (Zinc copper carbonate hydroxide; Zincrosasite), Na3
(Ca,Mn)2(CO3)3F (Sodium calcium manganese carbonate
?uoride hydroxide; Rouvilleite), (Na,Ca)4Zr2Ti(CO3)4O4
rium lanthanum yttrium carbonate ?uoride; Bastnasite), (Ba,
(Sodium calcium Zirconium titanium carbonate oxide; Sabi
Sr)6(Ca,Mn)6Mg(CO3)l 3 (Barium strontium calcium manga
naite), (Zn,Mg,Mn)4Zn3(CO3)2(OH)1O (Zinc magnesium
nese magnesium carbonate; Benstonite), YBaZCu3 (OH),€CO3
(Yttrium barium copper hydroxide carbonate), CaAl2(CO3)2
(OH)4.3H2O (Hydrated calcium aluminum carbonate
manganese carbonate hydroxide; Sclarite), Ca2Mgll(CO3)9
(HCO3)4(OH)4.6H2O (Hydrated calcium magnesium car
hydroxide; Alumohydrocalcite), CaAl2(CO3)2(OH)4.6H2O
bonate Bicarbonate Hydroxide; Sergeevite), Mg6Fe2CO3
(OH)l6.4H2O (Hydrated magnesium iron carbonate
(Hydrated calcium aluminum carbonate hydroxide; Para-alu
hydroxide; Sjogrenite), (Sr,Ca)Al2(CO3)2(OH)4.H2O (Hy
mohydrocalcite), Mg6Cr2(CO3)(OH)l6.4H2O (Hydrated
magnesium chromium carbonate hydroxide; Barbertonite),
Na7AlH2(CO3)4F4 (Sodium aluminum carbonate hydroxide
?uoride; Barentsite), K2Mg(CO3)2.4H2O (Hydrated potas
sium magnesium carbonate; Baylissite), (Ca,Pb)Bi2(CO3)
202 (Calcium lead bismuth carbonate oxide; Beyerite), Bi2
(CO3)O2 (Bismuth carbonate oxide; Bismutite), Ca2(CO3)F2
(Calcium carbonate ?uoride; Brenkite), Mg6Fe(CO3)(OH) l3.
4H2O (Hydrated magnesium iron carbonate hydroxide;
drated strontium calcium aluminum carbonate hydroxide;
Strontiodresserite), Pb4SO4(CO3)2(OH)2 (Lead sulfate car
bonate hydroxide; Leadhillite; Susannite), NaPb2(OH)
(CO3)2 (Sodium lead carbonate hydroxide), Hgl6(Ni,Mg)6
(H3O)8(CO3)12.3H2O (Hydrated mercury nickel magnesium
carbonate oxide hydroxide; SZymanskiite), NaCa2Al4(CO3)
4(OH)8Cl (Sodium calcium aluminum carbonate hydroxide
chloride; Tunisite), Na6Mg2(CO3)4SO4 (Sodium magnesium
carbonate sulfate; Tychite), Na2(Sr,Ca)3Zr(CO3)6.3H2O
Brugnatellite), K2Ca(CO3)2 (Potassium calcium carbonate;
Butschliite), Mg6Cr2CO3(OH)l6.4H2O (Hydrated magne
(Hydrated sodium strontium calcium Zirconium carbonate;
Weloganite), Ni3(CO3)(OH)4.4H2O (Hydrated nickel car
sium chromium carbonate hydroxide; Stichtite), Fe4Al2(OH)
l 2CO3 .3H2O (Hydrated iron aluminum carbonate hydroxide;
Caresite), Na2Cu(CO3 )2 .3H2O (Hydrated sodium copper car
bonate hydroxide; Zaratite), (Na,K)2Ca(CO3)2 (Sodium
potassium calcium carbonate; Zemkorite), Mn26As18O5O
(OH)4CO3 (Armangite), K5Na5(Ce,Ca)12Si28O7O(OH)2
(CO3)8.8H2O (Ashcroftine-(Ce)), K5Na5(Y,Ca)l2Si28O7O
(OH)2(CO3)8.8H2O (Ashcroftine-(Y)), Pb4(CO3)Cl6.H2O
(BarstoWite), CeZFe (CO3)(Si2O7) (Biraite-(Ce)), Na3Fe
bonate; Chalconatronite), Mn4Al2(CO3)(OH)l2.3H2O (Hy
drated manganese aluminum carbonate hydroxide; Charma
rite), NaAl(CO3)(OH)2 (Sodium aluminum carbonate
hydroxide; DaWsonite), CaMg3 (CO3)4 (Calcium magnesium
carbonate; Huntite), BaMg(CO3)2 (Barium magnesium car
bonate; Norsethite), PbAl2(CO3)2(OH)4.(H2O) (Hydrated
lead aluminum carbonate hydroxide; Dundasite), NaZMg
(CO3)2 (Sodium magnesium carbonate; Eitelite), K2Ca
(CO3)2 (Potassium calcium carbonate; Fairchildite), Cu5
(CO3)3(OH)4.6H2O (Hydrated copper carbonate hydroxide;
Georgeite), Mg6Al2(CO3)(OH)16.4H2O (Hydrated magne
sium aluminum carbonate hydroxide; Hydrotalcite), MgzAl2
(CO3)4(OH)2.l5H2O (Hydrated magnesium aluminum car
bonate hydroxide; lndigirite), BaAl2(CO3)2(OH)4.H2O
(Hydrated barium aluminum carbonate hydroxide; Dres
serite; Hydrodresserite), NaNi4(CO3)3(OH)3.3H2O (Hy
drated sodium nickel carbonate hydroxide; Kambaldaite),
CaBi(CO3)OF (Calcium bismuth carbonate oxide ?uoride;
Kettnerite), (Mn,Zn)7(CO3)2(OH)1O (Manganese Zinc car
bonate hydroxide; Loseyite), Pb 4SO4(CO3)2(OH)2 (Lead sul
fate carbonate hydroxide; macphersonite), Mg6Al2(CO3)
(OH)l6.4H2O (Hydrated magnesium aluminum carbonate
hydroxide; Manasseite), Na2Ca(CO3)2 (Sodium calcium car
bonate; Natrofairchildite; Nyerereite), Na2Ca(CO3)2.5H2O
(Hydrated sodium calcium carbonate; Gaylussite), Na2Ca2
(CO3)3, (Sodium calcium carbonate; Shortite), Na2Ca(CO3)
2.2H2O (Hydrated sodium calcium carbonate; Pirssonite),
NaCa3(CO3)2F3.H2O (Hydrated sodium calcium carbonate
?uoride; Sheldrickite), Na3Mg(CO3)2Cl (Sodium magne
sium carbonate chloride; Northupite), (Sr,Ca,Ba)(CO3)2
(Strontium calcium barium carbonate; Olekminskite), Mg2
(PO4)(CO3) (Bonshtedtite), Ca4MgB4O6(OH)6(CO3)2 (Bor
carite), Na3Mg(PO4)(CO3) (Bradleyite), Zn3(CO3,SO4)
(0H)4 (Bn'anyoungire), PbhxMgisusnAnsoul(B03)
(BO3,AsO4)(CO3)(OH,O)7 (x<0.5) (Britvinite), Na6(CO3)
(S04)2 (Burkeite), Na2(Ba,Sr)2(Fe,Mn)TiSi2O7(CO3)(OH)
3F (Bussenite), Na3(Ca,REE,Sr)3(CO3)5 (Calcioburbankite),
Were REE is for any rare earth element like scandium,
yttrium, lanthanum, cerium, praseodymium, neodymium,
promethium, samarium, europium, gadolinium, terbium,
dysprosium, holmium, erbium, thulium, ytterbium, or lute
tium), Pb5Cu2(CO3)(SO4)3(OH)6 (Caledonite), Cu2Mg2
(CO3)(OH)6.2H2O (Callaghanite), Cu4Al2[HSbO4,SO4]
(OH)l0(CO3).2H2O (Camerolaite), Mg2(CO3)(HBO3).
5H2O (Canavesite), Na6Ca2Al6Si6O24(CO3)2 (Cancrinite),
Ca2Mg(CO3)2B2(OH)8.4H2O (Carboborite), Ca5(PO4,CO3)
3F (Carbonate-?uorapatite), Ca5(PO4,CO3)3(OH) (Carbon
ate-hydroxylapatite), Cu4Al2(CO3,SO4)(OH)l2.2H2O (Car
bonatecyanotrichite), KNa4Ca4Si8Ol8(CO3)4(OH,F).H2O
(Carletonite), Ca3Ge(OH)6(SO4)(CO3).l2H2O (Carraraite),
(Ni,Cu)14Al9(SO4,CO3)6(OH)43.7H2O,
(Carrboydite),
Y2(Ca,Gd)2Si4OlO(CO3)3(H2O,O,OH).3H2O (Caysichite
(Y)), Ca,Mg)3Si(OH)6(SO4,CO3)2.9H2O, (Chelyabinskite),
Mg2(CO3)Cl(OH).3H2O (Chlorartinite), (Mg,Fe)4Al2(OH)
l2(Cl2,CO3).2H2O (Chlormagaluminite), Fe2(CO3)(OH)2,
(Chukanovite), (Cu,Zn)3(CO3)(OH)4.4H2O (Claraite), Hg3
(CO3)(OH).2H2O (Clearcreekite), Mg1OFe2(CO3)(OH)24.
2H2O (Coalingite), Ni6Co2(CO3)(OH)16.4H2O (Comblain
ite), Na3Sr(PO4)(CO3) (CraWfordite), (Sr,Ca,Ba)3(Ce,La)
US 2013/0017388 A1
Jan. 17,2013
uranyl carbonate hydroxide; Znucalite), Sr(Ce,La)(CO3)2
Lokkaite-(Y)),
(OH).H2O (Hydrated strontium cerium lanthanum carbonate
barium sodium calcium uranium yttrium carbonate; Mck
hydroxide; Ancylite-(Ce), orAncylite-(La)), BaNaCe2(CO3)
Fluoride;
elveyite), (Ba,Sr)(Ca,Na,Nd,REE)(CO3)2.3—lOHZO (Mck
elVeyite-(Nd)), NaCa(Ba,Sr)3(§CREE)(CO3)6.3H2O (Mck
Baiyuneboite-(Ce)), (La,Ce,Y)(CO3)F (Lanthanum cerium
yttrium carbonate ?uoride; Bastnasite-(La Bastnasite-(Ce),
or Bastnasite-(Y)), (Na,Ca)3 (Sr,Ba,Ce)3 (CO3)5 (Sodium cal
lanthanum carbonate ?uoride; Parisite-(Ce)), Ca(Nd,Ce,La)
2(CO3)3F2 (Calcium neodymium cerium lanthanum carbon
ate ?uoride; Parisite-(Nd)), (Na,Mn,Fe)l5(Y,REE)2(CO3)9
4F
(Sodium
barium
cerium
carbonate
cium strontium barium cerium carbonate; Burbankite),
elVeyite-(Y)),
Ba3Na(Ca,U)Y(CO3)6.3H2O
Ca(Ce,La)2(CO3)3F2
(Hydrated
(Calcium
cerium
(SO3F)Cl (Reederite-(Y)), Na3(Ce,La,Ca,Na,Sr)3(CO3)5
Ca(Ce,Nd,Sr)(CO3)2(OH).H2O (Hydrated calcium cerium
neodymium strontium carbonate hydroxide; Calcioancylite),
(Ce,La)2(CO3)3.4H2O (Hydrated cerium lanthanum carbon
Remondite-(Ce)), Na3 (La,Ce,Ca)3(CO3)5 (Remondite-(La)),
ate; Calkinsite-(Ce)), (Ca,Na)(Sr,Ce,Ba)(CO3)2 (Calcium
?uoride;
sodium strontium cerium barium carbonate; Carbocernaite),
(Magnesium iron cerium lanthanum neodymium carbonate;
(Sodium cerium lanthanum calcium strontium carbonate;
Ca2(Ce,La)3 (CO3)5F3 (Calcium cerium lanthanum carbonate
Rontgenite-(Ce)),
(Mg,Fe)(Ce,La,Nd)2(CO3)4
Ba3Ce2(CO3)5F2 (Barium cerium carbonate ?uoride;
Sahamalite), PbCu(Nd,Gd,Sm,Y)(CO3)3(OH).l.5H2O (Hy
Cebaite-(Ce)), Ba3(Nd,Ce)2(CO3)5F2 (Barium neodymium
drated lead copper neodymium gadolinium samarium yttrium
cerium carbonate ?uoride; Cebaite-(Nd)), Ba(Ce,La)2(CO3)
3P2 (Barium cerium lanthanum carbonate ?uoride; Cordylite
carbonate hydroxide; Schuilingite-(Nd)), Na3Y(CO3 )3 .3H2O
calcium barium cerium lanthanum phosphate carbonate
(Hydrated sodium yttrium carbonate; Shomiokite- (Y)), CaCe
(CO3)2F (Calcium cerium carbonate ?uoride; Synchysite
(Ce)), CaNd(CO3)2F (Calcium neodymium carbonate ?uo
hydroxide ?uoride; Daqingshanite-(Ce)), Sr3NaCaY(CO3)6.
ride; Synchysite-(Nd)), CaY(CO3)2F (Calcium yttrium
3(H2O) (Hydrated strontium sodium calcium yttrium carbon
carbonate ?uoride; Synchysite-(Y)), Y2(CO3)3.2—3H2O
ate; Donnayite-(Y)), (Ba,Sr)(Ca,Na,K,§LCe)(CO3)2 (Barium
(Hydrated yttrium carbonate; Tengerite-(Y)), Th(Ca,Ce)
(Ce)), (Sr,Ca,Ba)3(Ce,La)(PO4)(CO3)3_,€(OH,F),C (Strontium
strontium calcium sodium potassium yttrium cerium carbon
(CO3)2F2.3H2O (Hydrated thorium calcium cerium carbon
ate; EWaldite), Pb(Nd,La)(CO3)2(OH).H2O, Gysinite-(Nd)
ate ?uoride; Thorbastnasite), BaNa6Th(CO3)6.6H2O (Hy
(Hydrated lead neodymium lanthanum carbonate hydroxide),
NaY(CO3)F2 (Sodium yttrium carbonate ?uoride; Hor
Vathite-(Y)), BaCe(CO3)2F (Barium cerium carbonate ?uo
drated barium sodium thorium carbonate; Tuliokite),
Na2Ce2TiO2(SiO4)(CO3)2 (Sodium cerium titanium oxide
ride; Huanghoite-(Ce)), (Ce, La, Nd)CO3(OH, F) (Cerium
lanthanum neodymium carbonate hydroxide ?uoride;
Hydroxylbasnasite), (Ce, La, Nd)CO3OH (Cerium lantha
num neodymium carbonate hydroxide; Hydroxylcarbonate
(Nd)), (NaCa)3(Ba,Sr,Ce,Ca)3(CO3)5 (Sodium calcium
barium strontium cerium carbonate; Khanneshite), CaY2
(CO3)4.6H2O (Hydrated calcium yttrium carbonate; Kimu
raite-(Y)), (Ce,La,Nd)2(CO3)3.8H2O (Hydrated cerium lan
thanum neodymium carbonate; Lanthanite; Neodymite),
CaY4(CO3)7.9H2O (Hydrated calcium yttrium carbonate;
silicate carbonate; Tundrite-(Ce)), Na3(Nd,La)4(Ti,Nb)2
(SiO4)2(CO3)3O4(OH).2H2O (Sodium neodymium lantha
num titanium niobium silicate carbonate oxide hydroxide;
Tundrite-(Nd)), and other carbonate salts and hydrates, and
related acids and bases forms.
[0024] Contrary to carbonate salts and minerals Which
release carbon dioxide upon thermal decomposition, an
example for a reaction With other chemicals can be heating of
an intimate mixture of poWdered Zinc metal and calcium
carbonate, Which releases carbon monoxide (CO) according
to the folloWing reaction: Zn+CaCO3QZnO+CaO+COCgy
TABLE 2
Bicarbonate salts and minerals (releasing Water (H20)
and carbon dioxide (CO7) during thermal decompo ition)
Chemical name
Other names
Potassium hydrogen
carbonate
Potassium
bicarbonate,
Chemical
formula
(empirical)
Related compounds
KHCO3
Potassium acid
carbonate,
Bicarbonate of
potassium,
Kalicinite
Sodium hydrogen
carbonate
Sodium
NaHCO3
bicarbonate, Baking
soda, Bread soda,
Cooking soda,
Bicarbonate of
soda, Nahcolite
Magnesium hydrogen
Magnesium
carbonate
Calcium hydrogen
bicarbonate
Calcium
carbonate
bicarbonate
Rubidium hydrogen
Rubidium
carbonate
bicarbonate
Cerium hydrogen
Cerium
carbonate
bicarbonate
MgHCO3
Mg(HCO3)(OH)°2H2O (Hydrated magnesium
bicarbonate hydroxide; Nesquehonite)
CaHCO3
RbHCO3
CeHCO3
US 2013/0017388 A1
Jan. 17,2013
[0025] More bicarbonate minerals that can be used accord
ing to some embodiments of the invention may include HPb4
Cu4Si4Ol2(HCO3)4(OH)4Cl (Ashburtonite), (Na,Ce)(Y,
REE)(HCO3)(OH)3.4H2O (Thomasclarkite-(Y)), Na25Ba(Y,
Gd,Dy)2(HCO3)4(CO3)ll(SO4)2ClF2 (Mineevite-(Y)), and
other bicarbonate salts and hydrates, and related acids and
bases forms.
nitrate hydroxide; Gerhardtite), Cu3(NO3)(OH)5.2H2O (Hy
drated copper nitrate hydroxide; Likasite), (Ni,Cu)Al4(NO3,
SO4)2(OH)l2.3H2O (Hydrated nickel copper aluminum
nitrate sulfate hydroxide; Mbobomkulite), (Ni,Cu)Al4(NO3,
SO4)2(OH)l2.l4H2O (Hydrated nickel copper aluminum
nitrate sulfate hydroxide; Hydrombobomkulite), KAl7(NO3)
4Cl2(OH)l6.8H2O (Hydrated potassium aluminum nitrate
TABLE 3
Nitrates and nitrite salts and minerals (releasing nitrogen dioxide (N 02) and/or oxygen
(02), and/or nitrogen (N2) and/or Water (H2O) during thermal decomposition)
Chemical
formula
Chemical name
Other names
(empirical)
Related compounds and remarks
Lithium nitrate
Sodium nitrate
Nitratine, Nitratite,
LiNO3
NaNO3
LiNO2 (Lithium nitrite)
NaNO2 (Sodium nitrate)
KNO3
KNO2 (Potassium nitrite)
Nitronatrite, Soda
Niter
Potassium nitrate
Niter, Nitre,
Salpeter
Ammonium nitrate
NH4NO3
Decomposes to N2O(g) + H2O(g), or N2(g) +
Calcium nitrate
Ca(NO3)2
H2O<g> + O2<g>
Ca(NO3)2°4H2O (tetrahydrate calcium nitrate;
Magnesium nitrate
Mg(NO3)2
Cesium nitrate
Rubidium nitrate
CsNO3
RbNO3
Copper Nitrate
Cu(NO3)2
beryllium dinitrate
Strontium nitrate
Be(NO3)2
Sr(NO3)2
Nitrocalcite)
Mg(NO3)2°6H2O (hexahydrate magnesium
nitrate), Nitromagnesite
Cu2(NO3)(OH)3 (Rouaite), Cu(NO3)2°3H2O,
Cu(NO3)2°6H2O
Sr(NO3)2 °4H2O (Strontium nitrate
tetrahydrate)
Barium nitrate
Scandium nitrate
Chromium nitrate
Manganese nitrate
Iron nitrate
Nitrobarite
Ba(NO3)2
Sc(NO3)3
Manganese dinitrat
Cr(NO3)3
Mn(NO3)2
ferric nitrate
Fe(NO3)3
[Cr(H2O)6](NO3)3 °3H2O
Mn(NO3)2°4H2O (tetrahydrate)
Fe(NO3)3°9H2O (nonahydrate),
Fe(NO3)3°6H2O (hexahydrate)
Co(NO3)2
Co(NO3)2 °nH2O, (n = 2, 4, 6)
Nickel nitrate
Cobalt nitrate
Cobaltous nitrate
Ni(NO3)2
Ni(NO3)2°6H2O (hexahydrate)
Palladium nitrate
Silver nitrate
Pd(NO3)2
AgNO3
Zinc nitrate
Cadmium nitrate
Mercury nitrate
Aluminium nitrate
Lead(H) nitrate
Chlorine nitrate
Zn(NO3)2
Cd(NO3)2
Hg(NO3)2
Al(NO3)3
Pb(NO3)2
ClNO3
Gadolinium nitrate
Gd(NO3)3
Uranyl nitrate
UO2(NO3)2
Zn(NO3)2°6H2O (hexahydrate)
Cd(NO3)2 °4H2O
Hgd(NO3)2°H2O (monohydrate)
Al(NO3)3 °9H2O
Decompose to Cl2(g) + NO?g)
UO2(NO3)2°nH2O (n = 3, 6)
[0026] More nitrate minerals that can be used according to
some embodiments of the invention are Cul9Cl4(NO3)2(OH)
32.2H2O (Hydrated copper nitrate chloride hydroxide; But
tgenbachite), Na3 (SO4)(NO3).H2O (Hydrated sodium sulfate
nitrate hydroxide; Darapskite), Cu2(NO3)(OH)3 (Copper
chloride hydroxide; Sveite), (NH4,K)(NO3) (Ammonium
potassium nitrate; GWihabaite), K3Na7Mg2(SO4)6(NO3)2.
6H2O (Humberstonite), (Ni,Cu)Al4[(SO4),(NO3)2](OH)12.
3H2O (Nickelalumite), K3Na8Fe(SO4)6(NO3)2.6H2O (Un
gemachite), and other nitrate and nitrite salts and hydrates,
and related acids and bases forms.
US 2013/0017388 A1
Jan. 17,2013
TABLE 4
Iodate and periodate salts and minerals (releasing oxygen
(O2) or/and iodine (12) during thermal decomposition)
Chemical name
Other names
Lithium iodate
Sodium iodate
Chemical
formula
(empirical)
Related compounds
LiIO3
NaIO3
Potassium iodate
K103
Silver iodate
AgIO3
Barium iodate
Ba(IO3)2
Ba5(IO6)2
Ca(IO3)2
Ca(IO3)2°H2O (Hydrated Calcium Iodate;
Calcium iodate
Lautarite
KH(IO3)2 (Potassium hydrogen iodate)
Bruggenite)
Strontium iodate
Nickel iodate
Sr(IO3)2
Ni(IO3)2
Cesium periodate
Copper iodate
Cs(IO4)2
Cu(IO3)2
Ni(IO3)2°2H2O
Cu(IO3)(OH) (Copper iodate hydroxide; Salesite),
Cu3(IO3)6°2H2O, (Hydrated copper iodate;
Bellingerite)
[0027] More iodate minerals that can be used according to
some embodiments of the invention are Pb6(lO3)2Cl4O2
[0028] Other bromate and perbromate salts and hydrates,
and related acids and bases forms may be used according
(OH)2 (Lead iodate oxide chloride hydroxide; SchWartZem
some embodiments of the invention.
bergite), K6(Na,K)4Na6MglO(SO4)l2(IO3)l2.12H2O (Fuen
Zalidaite),
K6(Na,K)4Na6MglO(SeO4)12(IO3)l2.12H2O
(CarlosruiZite), Na6CaMg(IO3)6(CrO4)2.12H2O (George
ericksenite), Ca2(IO3)2(CrO4) (Dietzeite), Pb3Cl3(IO3)O
Chlorate and perchlorate salts and minerals (releasing oxygen
(Seeligerite), Na9(IO3)(SO4)4 (Hector?oresite), and other
(O2) or/and chlorine (Cl2) during thermal decomposition)
TABLE 6
iodate and periodate salts and hydrates, and related acids and
bases forms.
Chemical
formula
TABLE 5
Chemical name
(empirical)
Related compounds and remarks
Potassium chlorate
Sodium chlorate
Barium chlorate
Calcium chlorate
Ammonium chlorate
KClO3
NaClO3
Ba(ClO3)2
Ca(ClO3)2
NH4ClO3
KClO4 (Potassium perchlorate)
NaClO4 (Sodium perchlorate)
Ba(ClO4)2 (Barium perchlorate)
Ca(ClO4)2 (Calcium perchlorate)
NH4ClO4 (Ammonium perchlorate;
Bromate and perbromate salts and minerals (releasing oxygen
(0;) or/and bromine (Br?) during thermal decomposition)
Chemical name
Chemical
formula
(empirical)
Lithium bromate
LiBrO3
Sodium bromate
NaBrO3
Related compounds
Ba(BrO3)2 °H20,
NaBrO4 (Sodium perbromate)
Potassium bromate
Decomposes to Cl2(g) + N2(g) +
KBrO3
Magnesium bromate
Mg(BrO3)2
Calcium bromate
Strontium bromate
Barium bromate
Silver bromate
Cesium bromate
Rubidium bromate
Nickel bromate
Zinc bromate
Cadmium bromate
Ca(BrO3)2
Sr(BrO3)2
Ba(BrO3)2
AgBrO3
CsBrO3
RbBrO3
Ni(BrO3)2
Zn(BrO3)2
Cd(BrO3)2
Neodymium bromate
Praseodymium bromate
Nd(BrO3)3
Pr(BrO3)3
Nd(BrO3)3 °9H2O
Pr(BrO3)3°9H2O
Yttrium bromate
Thallium bromate
Y(BrO3)3
TlBrO3
Y(BrO3)3°9H2O
Lithium chlorate
LiClO3
Magnesium chlorate Mg(ClO3)2
LiClO4 (Lithium perchlorate)
Mg(ClO4)2 (Magnesium perchlorate),
Caesium chlorate
Rubidium chlorate
Silver chlorate
Thallium chlorate
Cs(ClO4)2 (Caesium perchlorate)
RbClO4 (Rubidium perchlorate)
AgClO4 (Silver perchlorate)
TlClO4 (Thallium perchlorate)
Mg(ClO4)2°6H2O
[0029]
Cs(ClO3)2
RbClO3
AgClO3
TlClO3
Other chlorate and perchlorate salts and hydrates,
and related acids and bases forms may be used according to
some embodiments of the invention.
US 2013/0017388 A1
Jan. 17, 2013
TABLE 7
Manganate (III, IV, or VI), dimanganate(III), permanganate and hypomanganate
salts and minerals releasing oxygen (07) during thermal decompo ition)
Chemical
formula
(empirical)
Chemical name
Potassium manganate
(VI)
K2MnO4
Barium manganate
BaMnO4
(V1)
Calcium manganate
(VI)
CaMnO4
Related compounds
KMnO4 (Potassium permanganate), K3MnO4 (Potassium
hypomanganate; Potassium manganate(V)), K6Mn2O6 (Potassium
dimanganate(III))
Ba(MnO4)2 (Barium permanganate)
Ca(MnO4)2 (Calcium permanganate; Acerdol), CaMnWO3 (Calcium
manganate (IV))
NaMnO4 (Sodium permanganate), NaMnO4°H2O (Sodium
permanganate monohydrate), NaMnIHO2 (Sodium manganate (III))
Sodium manganate
(VI)
Na2MnO4
Ammonium manganate
(NH4)2MnO4 NH4MnO4 (Ammonium permanganate; decomposes to MnO2 +
(VI)
Silver manganate
Ag2MnO4
N2(g) + H2O(g))
AgMnO4 (Silver permanganate)
(V1)
Lithium manganate
(III)
LiMnmO2
LiMn‘WZO4 (Lithium manganate (IV))
Lanthanum manganate
LaMnHIO3
(III)
[0032]
Other sulfate, sul?te, dithionite and thiosulfate salts
[0030] More manganate (III) minerals that can be used
according some embodiments of the invention are Lal_
and hydrates, and related acids and bases forms may be used
XCaXMnO3 (Lanthanum calcium manganate), La l_,€Ba,€MnO3
according to some embodiments of the invention.
(Lanthanum barium manganate), (Pr,Ca)MnO3 (Praseody
TABLE 10
mium calcium manganate), and other manganate (III, IV, or
VI), dimanganate(III), permanganate and hypomanganate
salts and hydrates, and related acids and bases forms.
Cyanates and thiocyanate salts and minerals (releasing carbon
dioxide (CO2), nitrogen oxides (NO and/or N02), and/or sul?ar dioxide
(S07) during thermal decomposition)
TABLE 8
Chromate and dichromate salts and minerals (releasing
oxygen (07) during thermal decomposition)
Chemical name
Chemical
formula
(empirical)
Potassium chromate
K2CrO4
Related compounds
K2Cr2O7 (Potassium dichromate;
Potassium bichromate; Bichromate
Chemical name
Chemical
formula
(empirical)
Related compounds
Sodium cyanate
Potassium cyanate
Rubidium cyanate
Cesium cyanate
Copper cyanate
NaOCN
KOCN
RbOCN
CsOCN
CuOCN
NaSCN (Sodium thiocyanate)
KSCN (Potassium thiocyanate)
RbSCN (Rubidium thiocyanate)
CsSCN (Cesium thiocyanate)
CuSCN (Copper thiocyanate)
Iron cyanate
Silver cyanate
Fe(OCN)2
AgOCN
Fe(SCN)2 (Iron thiocyanate)
AgSCN (Silver thiocyanate)
of potash; LopeZite)
[0033]
[0031]
Other chromate and dichromate salts and hydrates,
and related acids and bases forms may be used according to
Other cyanate and thiocyanate salts and hydrates,
and related acids and bases forms may be used according to
some embodiments of the invention.
some embodiments of the invention.
TABLE 11
TABLE 9
Fluorides salts and minerals (releasing ?uorine
(F7) during thermal decomposition)
Sulfate, sul?te, dithionite and thiosulfate salts and minerals
releasing sulfur dioxide SO2 during thermal decomposition
Ch?mic?l
formula
Chemical name
(empirical)
Barium sulfate
BaSO4
Iron Sulfate
F6504
Related compounds
If
u
4
Sodium dithionite Na2S2O4
Copper ?uoride
CuF2
Related compounds
[0034]
.
.
and bases forms can be used accordrng
to some embodlments
.
(Ferrohexahydrite), FeSO4°7H2O
(cb/lglgntesrg?z) C
If
C SO
formula
(empirical)
FeSO4°4H2O (RoZenite), FeSO4°5H2O
(Siderotil), FeSO4°6H2O
Opp?r Su ate
Chemical name
FeSO4°H2O lszomolPoklt?l’
.
C
Chgmica]
pglntalfydmi?) ( Opper Su ate
Other ?uorides salts and hydrates, and related acids
_
_
Ofthe lnventlon
[0035] In some embodiments of the invention, the micron
and/or sub-micron particles of the gas-releasing material are
present at a concentration of 0.05% W/W to 10% W/W. In other
embodiments of the invention, the concentration of the gas
forming material by Weigh of the total frost-imparting com
US 2013/0017388 A1
position is between 0.2 to 5% W/W. In some embodiments, the
concentration of the gas-releasing material is betWeen 0.2 to
0.5% W/W. In some embodiments, the gas-releasing concen
tration is less than 10% W/W of the total composition.
[0036] In some embodiments of the invention, the gas
forming material is CaCO3. In some embodiments of the
invention, the CaCO3 is present at a concentration of less than
2.5% W/W. In other embodiments of the invention, the con
centration of CaCO3 is betWeen 0.75 to 2.5% W/W. In other
embodiments of the invention, the concentration of the
CaCO3 is betWeen 1.0 to 1.8% W/W. In other embodiments of
the invention, the concentration of the CaCO3 is betWeen 1.0
to 1.3% W/W.
[0037] In some embodiments, the gas-forming material is
Ca(NO3)2. In some embodiments of the invention, the
Ca(NO3)2 is present at a concentration of less than 2.5% W/W.
In other embodiments of the invention, the concentration of
Ca(NO3)2 is betWeen 0.75 to 2.5% W/W. In other embodi
ments of the invention, the concentration of the Ca(NO3)2 is
betWeen 1.0 to 1 .8% W/W. In other embodiments of the inven
tion, the concentration of the Ca(NO3)2 is betWeen 1.0 to
1.3% W/W.
[0038] Frosting optical characteristics may include, but are
not limited to, light diffusing ability and/ or transparency (or
translucency) and/or transmittance and/ or opacity properties
of frosted pattern. The amount of the micron and/or sub
Jan. 17, 2013
or sulfur dioxide (SOZ), and/or iodine (I2) and/or bromine
(Br2), and/or chlorine (C12), and/or ?uorine (F2), and/or car
bon monoxide (CO), and various combination thereof folloW
ing decomposition or reaction With other materials; a ?xation
agent comprising an organic component; a glass frit; and a
liquid vehicle.
[0043]
The frost-imparting composition may further com
prise at least one additive, such as for example a Wetting
agent, a dispersing agent, a UV-curable agent, a defoamer, a
humectant, a rheology control agent, an anticorrosive agent,
an evaporation control agent, and an organic polymer as a
?xation agent.
[0044] In some exemplary embodiments of the invention,
the composition comprises a dispersing agent in a quantity
suf?cient to prevent particles agglomeration and phase sepa
ration. According to various exemplary embodiments of the
invention, the quantity can be adjusted to prevent phase sepa
ration for 7, 14, 21, 30, 60, 90, 120, 150, 180 or 360 days or
more. According to some exemplary embodiments of the
invention, increased concentration of dispersing agent con
tributes to a longer shelf life. According to other embodi
ments of the invention, a shorter shelf life is accepted in order
to avoid imparting undesirable characteristics to the compo
sition by increasing the amount of the dispersing agent in the
composition.
micron particles of the gas-forming material is adjusted in the
[0045]
range speci?ed above to in?uence one or more of these char
acteristics.
imparting composition may comprise at least one dispersant
or/ and Wetting agent. In some embodiments, the dispersant or
[0039]
It has unexpectedly founded that using micron and/
the Wetting agent is any one of DISPERBYK- 1 63 (solution of
or sub-micron particles of CaCO3 in a concentration of less
than 2.5 W/W % as the gas-releasing material provided to a
glass substrate an excellent frost appearance.
[0040] Thus, in some embodiments of the invention, there
high molecular Weight block copolymer With pigment af?nic
is provided a frost-imparting composition comprising less
In some embodiments of the invention, the frost
groups, in xylene/butyl/acetate/methoxypropylacetate 3/ 1/
1), BYKUMEN (solution of a loWer molecular Weight unsat
urated acidic polycarboxylic acid polyester and White spirit/
Isobutanol:2/1), SOLSPERSE 44000 (solution of active
than 2.5 W/W % micron and/or sub-micron particles of
CaCO3; a ?xation agent comprising an organic component; a
glass frit With or Without ceramic pigments; and a liquid
vehicle.
[0041] In some embodiments of the invention, the micron
and/or sub-micron particles of the gas-forming material are
subject to activation, i.e., to decompose or react to form gas
bubbles, above a speci?c temperature. In some exemplary
embodiments of the invention, the speci?c activation tem
perature is an inherent property of the gas-forming material.
Optionally, an additive can be provided to loWer the speci?c
polymeric dispersant in Water), EFKA-7500 (aliphatic poly
temperature in practice (although it should remain theoreti
cally constant). The activation temperature of this material
can include an organic polymeric material or inorganic mate
rial. The organic polymeric material is selected from acrylic
may vary betWeen 400° C. to 1000° C. For example, speci?c
resins, carboxylated acrylic resins, polyvynilpyrrolidone,
activation temperatures may be, for example, 400° C., 4500
C., 5000 C., 550° C., 600° C., 630° C., 650° C., 700° C., 800°
polyvinylbutyral, condensate of urea and aldehydes, polyvi
nyl resins, cellulose acetate butyrate, and mixtures thereof.
C., 900° C., or 1000° C. In some embodiments of the inven
Organic polymeric ?xation agents suitable for use in exem
plary embodiments of the invention include, but are not lim
tion, the activation temperature for yielding gas bubbles is
betWeen 580 to 760° C. In other embodiments of the inven
tion, the temperature is betWeen 600° C. to 700° C. In some
embodiments, the speci?c activation temperature can vary as
ether With acidic groups), BYK-358 (solution of polyacrylate
copolymer and alkyl benZenes) and BYK-341 (Solution of a
polyether modi?ed polydimethylsiloxane) or any combina
tion thereof. In some embodiments of the invention, the
amount of the dispersant, based on the total Weight of the
frost-imparting composition, may be betWeen 0 to 30% W/W.
[0046] In some embodiments of the invention, the compo
sition further comprises a ?xation agent to contribute to glass
or the ceramic substrate adhesion. According to various
exemplary embodiments of the invention, the ?xation agent
a function of the pressure conditions and/ or the additive con
ited to, polyvinylpyrolidone (PVP), polyvinylalcohol (PVA),
polyethylene oxide (PEO), polyvinyl butyral (PVB), polyeth
ylene glycols (PEG), starch, carboxymethyl cellulose
(CMC), methyl cellulose, aldehyde resin, gelatin, hydroxy
centration and/or the intended substrate and/ or the gas-form
ethyl cellulose (HEC) and hydroxypropyl cellulose (HPC).
ing material.
Inorganic ?xation agents suitable for use in exemplary
[0042]
embodiments of the invention include, but are not limited to,
According to some embodiments of the present
invention, the frost-imparting composition may include at
silica nanoparticles, titania nanoparticles, Zinc compound
least one gas-forming material, Which releases carbon diox
ide (CO2), and/or Water (H2O), and/or nitrogen oxides (NO
nanoparticles, and Zirconia nanoparticles. In some embodi
ments of the invention, the organic ?xation agent is LARO
and/ or NO2), and/or oxygen (O2), and/ or nitrogen (N2), and/
PAL A-81 (aldehyde resin).
US 2013/0017388 A1
[0047] In some exemplary embodiments of the invention,
the organic ?xation agent concentration, based on the total
Weight of the frost-imparting composition, is in the range of
0.1-10% W/W. Optionally, the ?xation agent concentration is
in the range of 0.1-2.0% W/W.
[0048] Optionally, the frost-imparting composition may
Jan. 17, 2013
above, thus imparting a partial UV curing capability for the
composition, Which is su?icient to cause ?xation of the
printed droplets, immediately after exposure to UV light (or
alternatively the liquid vehicle is composed of UV-curable
composition).
include at least one organic polymeric material, Which func
[0056] In some embodiments of the invention, the ink frost
imparting composition of the invention may comprise a least
tions as a ?xation agent enabling adhesion of the ink or the
one UV-curable monomer and/or oligomer, such as: SR-504
paste composition to the substrate prior the ?ring, in addition
(ethoxylated-4-nonyl phenol acrylate), SR-355 (ditrimethy
to a n inorganic component, Which is the glass frit particles
lolpropane tetra acrylate), CN-550 (methoxy polyethylene
glycol monomethacrylate), and any other UV-polymeriZable
functioning as an enamel component.
[0049] In some embodiments of the invention, the glass frit
is based on oxides chosen, for example, from silicon, lithium,
potassium, calcium, aluminum, lead, Zinc, bismuth, titanium,
Zirconium, sodium, boron, tin, vanadium, molybdenum,
acrylic or vinyl monomers and oligomers.
[0057] In some embodiments of the invention, the ink frost
imparting composition may comprise a least one photo-ini
tiator and photosensitiZer, such as: Luricin TPO (Diphenyl
magnesium and other oxides. In some embodiments of the
(2,4,6-trimethylbenZoyl)-phosphine oxide), Speedcure ITX
invention, the glass frit is B5317F (a bismuth-containing
(Isopropyl-9H-thioxanthen-9-one, 97%, mixture of 2 and 4
borosilicate glass frit).
isomers), and any other photo-initiator and/or photosensi
[0050]
tiZer.
[0058]
In some embodiments of the invention, the concen
tration of the inorganic enamel component, Which includes
the glass frit particles, may be in the range of 20% W/W to 90%
W/W. In some embodiments of the invention, the concentra
tion of the glass frit is in the range of 35-75% W/W. In other
embodiments of the invention, the concentration of the glass
frit particles is in the range of 40-50% W/W. Further according
to an embodiment of the present invention, the diameter of the
glass frit particles is less than 100 micron. In some embodi
ments, the diameter of the glass frit particles is in less than
3000 nm. In some embodiments, in Which the composition
may be suitable for inkjet printing, the diameter is in the range
of 100-1200 nm, optionally 100-800 nm.
[0051] According to some embodiments of the invention,
the liquid carrier or liquid vehicle is an organic solvent that is
selected from the group consisting of propylene glycol mono
methyl ether (PM), dipropylene glycol mono methyl ether
(DPM), propylene glycol mono methyl ether acetate (PMA),
diethylene glycol mono butyl ether (DB), propylene glycol
diacetate (PGDA), or any combination thereof.
[0052]
According to other embodiments of the invention,
the liquid carrier or liquid vehicle is Water or a combination of
Water and tWo or more of the above organic solvents provided
that the solubility of the gas-forming material in the compo
sition of the invention is less than 20%.
[0053] According to some embodiments of the invention,
the total amount of the liquid vehicle in the frost-imparting
composition may range from 10 to 80 W/W %. According to
other embodiments of the invention, the total amount of the
liquid vehicle may range from 30 to 70 W/W %. According to
other embodiments of the invention, the total amount of the
liquid vehicle may range from 40 to 60 W/W %.
[0054] It may be desirable to ?x the ink to the substrate
before the ?ring so as to improve the printing properties.
Addition of UV-curable agents may enable rapid ?xation of
UV-polymeriZable ink compositions can also con
tain UV stabiliZers selected from: Hydroquinone, Methylhy
droquinone, Hydroquinone bis(2-hydroxyethylen)ether,
Butylated hydroxyanisole or dihydroquinone monomethyl
ether, and any other UV stabiliZers.
[0059] In some exemplary embodiments of the invention,
the composition includes one or more pigments. The combi
nation of pigments With micron and/ or sub-micron particles
of gas-forming materials in a single composition may con
tribute to the ability to tint frosted patterns. Tinting With a
desire color can be achieved by selecting an appropriately
colored pigment. Since the color must be stable at the relevant
?ring temperature, pigments based upon metal salts (i.e.,
inorganic) are suitable for use in many exemplary embodi
ments of the invention. For example, cobalt salts can impart a
blue tint, iron oxide can impart a red tint, copper oxide or
mixed oxides can impart black tints, nickel-antimony-tita
nium oxides can impart a yelloW tint, and gold or silver salts
can be used to impart a gold or silver color, respectively.
According to some embodiments of the invention, the amount
of the inorganic pigments, based on the total Weight of the
frost-imparting composition, may range from 0.1 to 25%
W/W. According to other embodiments of the invention, the
total amount of the inorganic pigments may range from 0.3 to
10% W/W. According to other embodiments of the invention,
the total amount of the inorganic pigments may range from
0.5-5% W/W.
[0060] Further, according to embodiments of the present
invention, the diameter of the inorganic pigments is less than
50 micron. In other embodiments, the diameter of the inor
ganic pigments is in less than 3 micron. In some embodi
ments, like in inkjet printing, the diameter is in the range of
100-1000 nm, and in other embodiments, the diameter is in
the range of 50-700 nm.
the printed frosted pattern by exposing the surface-bearing
[0061]
ink droplets to UV radiation, after printing. The term “UV
curable agent” refers to a composition that can polymeriZe
upon application of UV irradiation. Typically, these are
photo-polymeriZable monomers or oligomers, together With
photo initiators and/or photosensitiZers. Since the UV curable
agents are organic molecules, they are burnt out during the
composition as described hereinabove is used in a process
?ring of the printed glass pattern.
[0055]
According to some embodiments, the UV-curable
In some exemplary embodiments of the invention, a
selected from the group consisting of screen and/or pad and/
or offset and/ or ?exographic and/or gravure printing, spray
and/or dip and/ or roller coating. In some exemplary embodi
ments of the invention, there is provided an ink printing
cartridge containing an ink frost-imparting composition as
described herein.
[0062] In some exemplary embodiments of the invention,
composition (monomers, oligomers, photoinitiators, photo
there is provided an article of manufacture that includes: an
sensitiZers) may be added to the composition described
ink frost-imparting composition also referred to in the appli
US 2013/0017388 A1
cation as frost appearance composition as described herein;
Jan. 17,2013
vation energy they Would release at least one of carbon diox
packaging material; and instructions for use, the instructions
ide (CO2), and/or Water (H2O), and/or nitrogen oxides (NO
specifying a temperature at Which the micron and/or sub
and/or NO2), and/ or oxygen (O2), and/ or nitrogen (N2), and/
or sulfur dioxide (SOZ), and/or iodine (I2) and/or bromine
(Br2), and/or chlorine (C12), and/or ?uorine (F2), and/or car
micron particles of the gas-forming material releases gas
bubbles Which are used for imparting frosted glass or ceramic
substrates.
[0063] In an embodiment of the invention, there is provided
a frosted glass or ceramic substrate printed With a pattern or
bon monoxide (CO).
[0068] According to some embodiments of the invention,
the gas-releasing material is CaCO3. According to some
image having a frost appearance by using the composition
exemplary embodiments of the invention, the CaCO3 is
described herein and the method and the printing process
described herein. Speci?cally, some embodiments of the
invention are based on the ?nding that it is possible to obtain
frosted patterns on a solid substrate surface (e. g. glass) using
present at a concentration of at less than 2.5% W/W.
a frost-imparting composition, Which includes at least one
react, yielding gas such as carbon dioxide (CO2), and/ or Water
(H20), and/ or nitrogen oxides (NO and/ or NO2), and/ or oxy
gas-forming material, Which is inactive in storage and during
the printing/coating time. i.e., the material doesn’t decom
pose or react to form gas bubbles. According to embodiments
of the invention, the frost-imparting composition is an ink jet
composition, Which is dispensed from an inkj et system. The
composition is selectively inkjet printed onto a solid substrate
surface and produces a frosted pattern thereupon When ?red at
a suitable temperature range.
[0064] Alternatively or additionally, some embodiments of
the invention can be used in coating (e.g. screen printing) or
[0069] Subsequent ?ring at a temperature of at least 4000 C.
causes the micron and/or sub-micron particles of the gas
forming material to undergo activation, i.e., to decompose or
gen (O2), and/or nitrogen (N2), and/or sulfur dioxide (SOZ),
and/or iodine (I2) and/ or bromine (Br2), and/or chlorine (C12),
and/or ?uorine (F2), and/or carbon monoxide (CO), and vari
ous combination thereof, Which provide the frosted pattern
applied on the solid substrate surface, e.g., a glass surface.
The process results in a foamy White or colored layer Which is
then removed by scrubbing or Washing so as to result in a
printing processes (eg inkj et printing) and/or to print a pat
frosted solid substrate, e.g., frosted glass or frosted ceramic.
[0070] In some embodiments of the invention, there is pro
vided a printing process that includes incorporating a frost
tern for imparting frosting onto a masked or unmasked sur
imparting composition including the micron and/or sub-mi
face. Alternatively or additionally, some embodiments of the
invention can be used in coating or printing processes onto ?at
cron particles of the gas-forming material into a printing
or curved, even or uneven, smooth or coarse, textured or
ing material using one of the above mentioned printing meth
non-textured, contoured or non-contoured glass or ceramic
substrate surface.
[0065] Embodiment of the invention includes, a method of
imparting a frost appearance to a solid substrate, Which may
be a glass or a ceramic substrate. The method may include
ods onto a solid substrate surface, e.g., a glass or ceramic
applying a frost-imparting composition as described herein
onto an unmasked solid substrate surface to form a pattern;
?ring the surface at the speci?c temperature at Which a micron
and/ or sub-micron particles of a gas-forming material/ s
yield/s gas bubbles, Which may be carbon dioxide (CO2),
apparatus; applying the composition including the gas-form
surface; ?ring of the surface at a temperature of at least at 4000
C. and above the activation temperature of the gas-forming
material, causing it to decompose or react to yield bubbles of
carbon dioxide (CO2), and/or Water (H2O), and/or nitrogen
oxides (NO and/or NO2), and/ or oxygen (O2), and/ or nitrogen
(N2), and/or sulfur dioxide (SOZ), and/or iodine (I2) and/or
bromine (Br2), and/ or chlorine (C12), and/or ?uorine (F2),
and/or carbon monoxide (CO), and various combination
thereof, Which provide the frosted pattern printed on the sur
and/ or oxygen (O2), and/or nitrogen (N2), and/or sulfur diox
ide (SOZ), and/or iodine (I2) and/or bromine (Br2), and/or
chlorine (C12), and/or ?uorine (F2), and/ or carbon monoxide
(CO), and various combination thereof. These gas bubbles
face. The process results in a foamy White or colored layer,
Which is then removed by scrubbing or Washing so as to result
in a frosted imitated solid substrate, e.g., glass or ceramic.
[0071] In some embodiments of the invention, there is pro
vided a printing process comprising incorporating a frost
provide the frosted pattern on the surface to obtain a White or
imparting composition including a CO2 precursor into a print
colored foamy and opaque layer on the solid substrate Which
may be a glass or a ceramic substrate; cooling and removing
precursor using one of the above mentioned printing methods
and/ or Water (H20), and/or nitrogen oxides (NO and/ or NO2),
ing apparatus; applying the composition including the CO2
the residual White or colored poWder Which accumulates on
the glass or the ceramic substrate surface at the end of the
onto a solid substrate surface, e. g., a glass or ceramic surface;
?ring process.
temperature of the CO2 precursor, causing it to decompose
and yield CO2 bubbles, Which provide the frosted pattern
[0066]
In some embodiments of the invention, the removal
?ring of the surface at a temperature above the activation
of the White or the colored poWder layer may be performed by
a moderate scrubbing process using a glass Washing machine
or by use of, for example, an abrasive hand pad folloWed by
printed on the surface. The process results in a foamy White or
Washing.
or ceramic.
[0067]
According to some embodiments of the invention, a
frost-imparting composition may include a gas releasing
material. The gas releasing material may include micron and/
or sub-micron particles of carbonate, bicarbonate, nitrate,
nitrite, iodate, periodate, bromate, perbromate, chlorate, per
chlorate, ?uoride, manganate, dimanganate, permanganate,
hypomanganate, chromate, dichromate, sulfate, sul?te,
dithionite, thiosulfate, cyanate, thiocyanate or any combina
tion thereof. Upon heating these compound above their acti
colored layer, Which is then removed by scrubbing or Washing
so as to result in an imitated frosted solid substrate, e.g., glass
[0072] In some embodiments of the invention, there is pro
vided a printing process comprising incorporating an ink
fro st-imparting composition including the CO2 precursor into
a printing apparatus, Wherein the CO2 precursor is present at
a concentration of less than 2.5% W/W; applying the compo
sition including the CO2 precursor onto a solid substrate sur
face, e.g., a glass or ceramic surface; ?ring of the surface at a
temperature above the activation temperature of the CO2
precursor, causing the it to undergo decomposing to yield
US 2013/0017388 A1
CO2, Which provide the frosted pattern printed on the surface.
Jan. 17, 2013
Materials and Methods
[0080] The folloWing materials Were used in the formula
The process results in a foamy White or colored layer, Which
is then removed by scrubbing or Washing so as to result in a
frosted solid substrate, e.g., glass or ceramic.
tions described in examples beloW:
[0081] Glass frit B5317F (bismuth-containing borosilicate
[0073]
frit) from Johnson Matthey;
[0082] DPM (dipropylene glycol methyl ether) from
In some exemplary embodiments of the invention,
there is provided a printing process comprising incorporating
pattern on a solid substrate, e.g., glass or ceramic, surface
Gadot, Israel;
[0083] PGDA (propylene glycol diacetate) from Sigma
Aldrich;
[0084] DOWANOL DB (diethylene glycol butyl ether)
using the ink frost-imparting composition; ?ring the surface
from DoW Chemicals;
a ink frost-imparting composition that includes at least one
gas-forming material into a printing apparatus; printing a
at a temperature above the activation temperature of the gas
[0085] DOWANOL PM (propylene glycol methyl ether)
forming material so that it undergoes activation, i.e., decom
posing or reaction, to yield gas bubbles, Which foam the
from DoW Chemicals;
pattern on the surface; and removing the White or colored
layer formed on the surface.
[0074] Optionally, a composition according to one or more
embodiments of the invention described above can be used in
inkjet printing. The term “inkj et printing” as used herein
refers to drop on demand inkjet printing and continuous ink
jet printing.
[0075]
Alternatively or additionally, a composition accord
ing to one or more embodiments of the invention described
above can be used in screen and/or pad and/or offset and/or
?exographic and/ or gravure printing, spray and/or dip and/or
roller coating.
[0076] Optionally, a particular printing method being con
templated can contribute to formulation considerations. For
example, for application in drop on demand inkj et printing, an
exemplary frost-imparting composition containing a micron
and/ or sub-micron particles of a gas-forming material might
be formulated With a viscosity in the range of 10-30 cP,
optionally 15-25 cP, at jetting temperature of about 300 C.
LoW viscosity contributes to an ability to form small droplets
When exiting the noZZle, but may reduce pattern resolution by
causing the spreading of the applied composition on the sub
strate. In some embodiments, a composition With the same
micron and/or sub-micron particles of the gas-forming mate
rial formulated for continuous ink jet printing may be forrnu
lated With a viscosity in the range of 1-10 cP, optionally 3-6
cP, at jetting temperature.
[0077] The viscosity of the frost-imparting composition
[0086] DOWANOL PMA (propylene glycol methyl ether
acetate) from DoW Chemicals;
[0087] Calcium carbonate from Chemorad Chemicals;
[0088] Calcium nitrate from Sigma-Aldrich;
[0089] Pigment Black 28 (Copper Chromite Black Spinel);
[0090] Pigment Red 101 (iron oxide);
[0091]
BYK-341 (solution of a polyether modi?ed poly
dimethylsiloxane) from BYK-Chemie;
[0092] BYK-358 (solution of polyacrylate copolymer and
alkyl benZenes) from BYK-Chemie;
[0093] Efka 7500 (aliphatic polyether With acidic groups)
from BASF;
[0094] Disperbyk-163 (solution of high molecular Weight
block copolymer With pigment af?nic groups, in xylene/bu
tyl/acetate/methoxypropylacetate 3/ 1/ 1) from BYK-Chemie;
[0095] BYKUMEN (solution of a loWer molecular Weight
unsaturated acidic polycarboxylic acid polyester and White
spirit/isobutanol:2/ 1) from BYK-Chemie;
[0096]
SOLSPERSE 44000 (solution of active polymeric
dispersant in Water) from LubriZol;
[0097] JONCRYL 77 (acrylic polymer emulsion) from
BASF;
[0098] LUCIRIN TPO (2,4,6-trimethylbenZoyldiphe
nylphosphine oxide) from BASF;
[0099] SPEEDCURE ITX (2-isopropyl Thioxanthone)
from Lambson;
[0100] CN-550 (amine modi?ed polyether acrylate,) from
Sartomer;
[0101] SR-355 (ditrimethylolpropane tetraacrylate,) from
Sartomer;
[0102]
Screen-printing medium ST725 from Johnson Mat
they, Holland;
can be varied by adjusting the nature and/or amount of the
?xation agent and/ or the inorganic enamel component and/or
[0103] LAROPAL A-81 (aldehyde resin) from BASF;
the dispersant and/or the liquid vehicle. According to some
360,000) from Sigma-Aldrich;
exemplary embodiments of the invention, adjustments in the
viscosity contribute to pattern formation by affecting spread
[0105] Unless otherWise speci?ed, percentages (%) of
ingredients are W/W (Weight per Weight).
Example 1
ing or diffusion of an applied pattern prior to ?ring. Thus,
according to some exemplary embodiments of the invention,
a greater viscosity contributes to a higher pattern resolution
[0104]
PVP 360 (Polyvinylpyrrolidone, average mol Wt
Frost-Imparting Inkjet Solvent-Based Ink
Composition
and a loWer viscosity contributes to a reduced pattern resolu
tion (e.g. blurring).
[0106]
[0078]
micron particles of a carbonate salt as gas-forming material in
Various aspects of the invention are described in
greater detail in the folloWing Examples, Which represent
embodiments of this invention, and are by no means to be
In order to demonstrate the feasibility of using sub
solvent-based inkjet ink, the folloWing formulation, set forth
in table 11, Was prepared.
interpreted as limiting the scope of this invention.
EXAMPLES
[0079] Reference is noW made to the folloWing examples,
Which together With the above description, illustrate the
invention in a non limiting fashion.
TABLE 11
Component
Glass frit B5317F
Calcium carbonate
DOWANOL DB
Weight percentage (%)
32.60
1.20
14.30
US 2013/0017388 A1
Jan. 17, 2013
14
(thickness: 4 mm) by screen printer (using a 90T polyester
TABLE 1 1 -continued
screen) and dried at 150° C. for 10 minutes.
Component
Weight percentage (%)
DOWANOL PM
PGDA
EFKA 7500
LAROPAL A-81
BYK-35 8
BYK-341
DPM
[0111] The printed glass substrate Was heated in a furnace
at a temperature range of 660-665° C. for ?ve minutes, alloW
9.20
6.70
2.45
1.25
0.45
0.01
31.84
ing melting and sintering of the glass frit and burning of the
organic components. While the glass frit melted to form an
enamel coating layer on top of the printed glass, the CaCO3
Was decomposed to yield CO2 bubbles, Which are emitted
during the ?ring process, resulting in a relatively foamy White
and opaque layer. After cooling doWn the ?red glass, the
[0107] This ink Was prepared by mixing all the solvents, the
organic ?xation agent, the dispersant and the Wetting agent,
residual White poWder Which accumulated on the glass sur
face Was removed by a moderate scrubbing process using a
till a homogenous solution Was obtained. The glass frit and
suspension of the calcium carbonate in solvent, Which Was
milled for three hours in a bead mill (DINO-MILL MULTI
LAB, WAB; equipped With 0.5-0.7 mm beads size), Were
stepwise added to the previous solution While stirring at a
by use of an abrasive hand pad folloWed by Washing the glass
in Water. After air drying of the glass surface, a frost appear
high shear rate (using a high shear mixer) for 30 minutes. The
ink formulation Was ?ltered through 3-micrometer ?lter (F SI)
Example 3
glass Washing machine (LV-1500, POLYGLASS) or simply
ance, resulting in a very loW transparency, is obtained.
and then applied by an inkjet printer (Dip-Tech, model
GLASSJET PRO 24 PH) onto a ?at glass substrate (thick
ness: 4 mm) and dried at 120° C. for 10 minutes.
[0108] The printed glass substrate Was heated in a furnace
at a temperature range of 660-665° C. for three minutes,
alloWing melting and sintering of the glass frit and burning of
the organic components (i.e. the solvents, the dispersants, the
Wetting agents, and the other polymers and surface active area
materials). While the glass frit Was melted to form an enamel
coating layer on top of the printed glass, the CaCO3 Was
decomposed to yield CO2 bubbles, Which are emitted during
the ?ring process, resulting in a relatively foamy White and
opaque layer. After cooling doWn the ?red glass, the residual
White poWder Which accumulated on the glass surface Was
removed by a moderate scrubbing process using a glass Wash
ing machine (LV-1500, POLYGLASS) or simply by use of an
abrasive hand pad folloWed by Washing the glass in Water.
After air drying of the glass surface, a frost appearance,
resulting in a very loW transparency, is obtained.
Frost-Imparting Screen Printing Water-Based Ink
Composition
[0112]
In order to demonstrate the feasibility of using
micron particles of a nitrate salt as gas-forming material in
Water-based ink for screen printing process, the folloWing ink
formulation, set forth in table 13, Was prepared.
TABLE 13
Component
Glass frit B5317F
Calcium nitrate
JONCRYL 77
PVP 3 60
Water
SOLSPERSE 44000
DOWANOL DB
Weight percentage (%)
66.55
1.25
16.40
6.00
3.40
1.20
5.20
Example 2
Frost-Imparting Screen Printing Solvent-Based Ink
Composition
[0109]
In order to demonstrate the feasibility of using
micron particles of a carbonate salt as gas-forming material in
solvent-based ink for screen printing process, the folloWing
ink formulation, set forth in table 12, Was prepared.
the solvents. This blend Was thoroughly mixed and dispersed
by high shear mixer for 15 minutes. The ink formulation Was
printed onto a ?at glass substrate (thickness: 4 mm) by screen
printer (using a 90T polyester screen) and dried at 130° C. for
15 minutes.
[0114] The printed glass substrate Was heated in a furnace
at a temperature of 670° C. for tWo minutes, alloWing melting
TABLE 12
Component
[0113] This paste formulation Was prepared by blending
the glass frit, the calcium nitrate, the polymer emulsion, and
Weight percentage (%)
and sintering of the glass frit and burning of the organic
Glass frit B5317F
Calcium carbonate
74.1
2.5
components. While the glass frit melted to form an enamel
Screen-printing medium ST736
23.4
[0110] This paste formulation Was prepared by blending
the glass frit With the screen-printing medium. A suspension
of the calcium carbonate in solvent, Which Was milled for
three hours in a bead mill (DINO-MILL MULTI-LAB, WAB;
coating layer on top of the printed glass, the CaCO3 Was
decomposed to yield CO2 bubbles, Which are emitted during
the ?ring process, resulting in a relatively foamy White and
opaque layer. After cooling doWn the ?red glass, the residual
White poWder Which accumulated on the glass surface Was
removed by a moderate scrubbing process using a glass Wash
ing machine (LV-1500, POLYGLASS) or simply by use of an
equipped With 0.5-0.7 mm beads siZe), Was added to the
abrasive hand pad folloWed by Washing the glass in Water.
previous solution While stirring using a mixer) for 15 minutes.
After air drying of the glass surface, a frost appearance,
resulting in a very loW transparency, is obtained.
The ink formulation Was printed onto a ?at glass substrate
US 2013/0017388 A1
Jan. 17, 2013
Example 4
Frost-Imparting UV-Curable Inkj et Solvent-Based
Were also prepared, by incorporating at least one pigment into
the ink compositions as described in Table 15.
Ink Composition
[0115]
TABLE 15
In order to demonstrate the feasibility of using sub
micron particles of a carbonate salt as gas-forming material in
Component
UV-curable inkjet ink, the following ink formulation, set
Pigment Black 28 (Copper
Chromite Black Spinel)
forth in table 14, Was prepared.
TABLE 14
Component
Weight percentage (%)
Glass frit B5317F
Calcium carbonate
DOWANOL DB
DOWANOL PM
PGDA
EFKA-7500
LAROPAL A-81
BYK-35 8
BYK-341
DPM
LUCIRIN TPO
SPEEDCURE ITX
CN-550
SR-355
32.60
1.20
11.30
9.20
6.70
2.40
1.00
0.25
0.01
25 .34
2.50
1.00
4.00
2.50
[0116] This ink formulation Was prepared by mixing all the
solvents, the organic ?xation agent, the dispersant, and the
Wetting agent, folloWed by addition of the UV additives
(monomers, oligomers, and photo-initiators), till a homog
enous solution Was obtained. The glass frit and suspension of
the calcium carbonate in solvent, Which Was milled for 3
hours in a bead mill (DINO-MILL MULTI-LAB, WAB;
equipped With 0.5-0.7 mm beads siZe), Were stepWise added
to the previous solution While stirring at a high shear rate
(using a high shear mixer) for 30 minutes. The ink formula
tion Was ?ltered through 3-micrometer ?lter (PSI) and then
applied by an R&D inkjet printer machine prototype onto a
?at glass substrate (thickness: 4 mm). Immediately after the
printing process the printed glass Was exposed to UV light
(365 nm, 400W) for 2-5 seconds thus causing rapid ?xation of
the inkjet ink drops on the glass substrate.
[0117]
After the UV hardening process the ink Was dried at
1200 C. for 10 minutes, folloWed by heating the printed glass
substrate in a fumace at a temperature range of 660-665° C.
Weight percentage (%)
Glass frit B5317F
Calcium carbonate
DOWANOL DB
DOWANOL PMA
PGDA
BYKUMEN
LAROPAL A-81
BYK-358
BYK-341
DPM
0.70
32.60
1.20
14.30
7.30
6.70
1.00
1.25
0.45
0.02
34.48
[0119] The ink formulation Was prepared by mixing all the
solvents, the organic ?xation agent, the dispersant and the
Wetting agent, till a homogenous solution Was obtained. The
glass frit and suspension of the calcium carbonate in solvent
Were stepWise added to the previous solution folloWed by
addition of black pigment, While stirring at a high shear rate
(using a high shear mixer) for 30 minutes. The ink formula
tion Was ?ltered through 3-micrometer ?lter (PSI) and then
applied by an inkjet printer (Dip-Tech; model GlassJet PRO
24 PH) onto a ?at glass substrate (thickness: 4 mm) and dried
at 1200 C. for 10 minutes.
[0120]
The printed glass substrate Was heated in a furnace
at a temperature range of 660-665° C. for 3 minutes, alloWing
melting and sintering of the glass frit and burning of the
organic components (i.e. the solvents, the dispersants, the
Wetting agents, and the otherpolymers and surface active area
materials). While the glass frit melted to form an enamel
coating layer on top of the printed glass, the CaCO3 Was
decomposed to yield CO2 bubbles, Which are emitted during
the ?ring process, resulting in a relatively foamy gray and
opaque layer. After cooling doWn the ?red glass, the residual
gray poWder Which accumulated on the glass surface Was
removed by a moderate scrubbing process using an abrasive
hand pad folloWed by Washing the glass in Water. After air
drying of the glass surface, a gray tinted frost appearance,
resulting in a very loW transparency, is obtained.
for 3 minutes. Thus alloWing burning of the organic compo
nents (i.e. the solvents, the dispersants, the Wetting agents,
Example 6
and the other monomers, polymers and surface active area
Colored Frost-Imparting Inkj et Solvent-Based Ink
materials) and melting and sintering of the glass frit. While
Composition
the glass frit melted to form an enamel coating layer on top of
the printed glass, the CaCO3 Was decomposed to yield CO2
bubbles, Which are emitted during the ?ring process, resulting
in a relatively foamy White and opaque layer. After cooling
[0121]
In addition to the ink formulation described in
Example 6, additional colored frost-imparting ink formula
tion is described in Table 16.
doWn the ?red glass, the residual White poWder Which accu
mulated on the glass surface Was removed by a moderate
TABLE 16
scrubbing process using an abrasive hand pad folloWed by
Washing the glass in Water. After air drying of the glass sur
Component
face, a frost appearance, resulting in a very loW transparency,
is obtained.
Pigment Red 101 (iron oxide)
Example 5
Colored Frost-Imparting Inkj et Solvent-Based Ink
Composition
[0118] In addition to the ink formulation described in
Example 1, colored formulations for providing a frost effect
Glass frit B5317F
Calcium carbonate
DOWANOL DB
DOWANOL PM
PGDA
EFKA-7500
DISPERBYK-163
LAROPAL A-81
Weight percentage (%)
1.00
32.60
1.20
14.30
9.20
6.70
1.00
0.55
1.25
US 2013/0017388 A1
Jan. 17,2013
16
glass surface, a gray, red, blue, green, yellow and orange
TABLE 16-continued
Component
Weight percentage (%)
BYK-35 8
BYK-341
DPM
0.45
0.01
31.74
[0122] The ink formulation was prepared by mixing all the
solvents, the organic ?xation agent, the dispersant and the
wetting agent, till a homogenous solution was obtained. The
glass frit and suspension of the calcium carbonate in solvent
were stepwise added to the previous solution followed by
addition of red pigment, while stirring at a high shear rate
(using a high shear mixer) for 30 minutes. The ink formula
tion was ?ltered through 3-micrometer ?lter (PSI) and then
applied by an inkjet printer (Dip-Tech; model GlassJet PRO
24 PH) onto a ?at glass substrate (thickness: 4 mm) and dried
at 120° C. for 10 minutes.
[0123] The printed glass substrate was heated in a furnace
at a temperature range of 660-665° C. for three minutes,
allowing melting and sintering of the glass frit and burning of
the organic components (i.e. the solvents, the dispersants, the
wetting agents, and the other polymers and surface active area
materials). While the glass frit melted to form an enamel
coating layer on top of the printed glass, the CaCO3 was
decomposed to yield CO2 bubbles, which are emitted during
the ?ring process, resulting in a relatively foamy pink and
opaque layer. After cooling down the ?red glass, the residual
pink powder which accumulated on the glass surface was
removed by a moderate scrubbing process using an abrasive
hand pad followed by washing the glass in water. After air
drying of the glass surface, a pink tinted frost appearance,
resulting in a very low transparency, is obtained.
Example 7
Colored Frost-lmparting lnkjet Process by Digital
Mixing
[0124]
In addition to the ink formulation described in
tinted frost appearance, resulting in a very low transparency,
is obtained.
[0126] While certain features of the invention have been
illustrated and described herein, many modi?cations, substi
tutions, changes, and equivalents will now occur to those of
ordinary skill in the art. It is, therefore, to be understood that
the appended claims are intended to cover all such modi?ca
tions and changes as fall within the true spirit of the invention.
What is claimed is:
1. A method of producing a substrate having a frosted
appearance, the method comprising:
applying a frost-imparting composition onto a ceramic
substrate to receive a coated substrate, wherein the com
position comprises a liquid vehicle, 20% by weight to
90% by weight of glass frit particles and less than 10%
by weight of at least one gas releasing material, inactive
below an activation temperature of at least 4000 C., the
gas releasing material comprised at least one of carbon
ate, bicarbonate, nitrate, nitrite, iodate, periodate, bro
mate, perbromate, chlorate, perchlorate, ?uoride, man
ganate, dimanganate, permanganate, hypomanganate,
chromate, dichromate, sulfate, sul?te, dithionite, thio
sulfate, cyanate, thiocyanate compound or any combi
nation thereof; and
?ring the coated substrate to produce the frosted appear
ance of the substrate at a ?ring temperature of above
400° C., wherein the temperature is chosen to be above
the activation temperature of the gas -releasing material,
above which the gas-releasing material yields gas
bubbles and above a temperature that causes the glass
frit particles to behave as a viscous liquid.
2. The method of claim 1, further comprising:
removing a powder layer that is formed on the coated
substrate during the ?ring.
3. The method of claim 1, further comprising:
prior to ?ring, heating the coated substrate at a temperature
above the boiling point of the liquid vehicle and below
the ?ring temperature.
Example 6, a digital mixing process was performed by using
4. The method of claim 1, wherein upon ?ring the gas
an inkjet printer (Dip-Tech; model Glass] et PRO 24 PH) with
the ink formulation of Example 1 using combination of six
releasing material releases gas bubbles of at least one of
different commercial ceramic inks (DIP SPECTRUM, Dip
Tech). The ceramic inks which have been used are colors:
Black, Red, Blue, Green, Yellow, and Orange. For each one of
the colors, the digital mixing in the inkjet printer was per
formed by placing side by side (resolution of ca. 70 um) small
drops of the ink formulation of Example 1 and of the ceramic
ink on a ?at glass substrate (thickness: 4 mm).
[0125] The printed glass was dried at 120° C. for 10 min
utes and heated in a fumace at a temperature range of 660
665° C. for three minutes, allowing melting and sintering of
the glass frit and burning of the organic components (i.e. the
solvents, the dispersants, the wetting agents, and the other
polymers and surface active area materials). While the glass
frit melted to form an enamel coating layer on top of the
printed glass, the CaCO3 was decomposed to yield CO2
bubbles, which are emitted during the ?ring process, resulting
in a relatively foamy colored and opaque layer. After cooling
carbon dioxide (CO2), water (H2O), nitrogen oxides (NO
and/or NO2), oxygen (O2), nitrogen (N2), sulfur dioxide
(SOZ), iodine (l2) bromine (Br2), chlorine (C12), ?uorine (F2),
carbon monoxide (CO) and any combination thereof.
5. The method of claim 1, wherein the glass frit particles
are micron or sub-micron particles.
6. The method of claim 1, wherein the at least one gas
releasing material is calcium carbonate (CaCO3) and the ?r
ing temperature is between 580° C. to 760° C.
7. The method of claim 1, wherein the frost-imparting
composition further comprises a dispersing agent, a wetting
agent, a UV-curable agent, an organic ?xation agent or any
combination thereof.
8. The method of claim 1, wherein the composition further
comprises at least one pigment.
9. The method of claim 1, wherein the substrate is glass.
down the ?red glass, the residual colored powder which accu
mulated on the glass surface was partially removed by a
moderate scrubbing process using an abrasive hand pad fol
10. The method of claim 1, wherein the frost-imparting
composition is an ink jet composition and applying the frost
imparting composition onto the ceramic substrate comprises
dispensing the frost-imparting composition from an inkjet
lowed by washing the glass in water. After air drying of the
system.
US 2013/0017388 A1
Jan. 17,2013
17
11. A article comprising:
a ceramic substrate; and
a coating composition that, prior to ?ring, comprises a
liquid vehicle, 20% to 90% by Weight of glass frit par
14. The article of claim 11, Wherein the frost-imparting
composition further comprises a dispersing agent, a Wetting
agent, a UV-curable agent, an organic ?xation agent or any
combination thereof.
15. A frost imparting composition comprising:
ticles and less than 10% by Weight of at least one gas
releasing material, inactive beloW an activation tempera
ture of at least 4000 C., the gas releasing material com
a liquid vehicle;
20% to 90% by Weight of glass frit particles; and
less than 10% by Weight of at least one gas releasing
prised of carbonate, bicarbonate, nitrate, nitrite, iodate,
material, inactive beloW an activation temperature of at
periodate, bromate, perbromate, chlorate, perchlorate,
?uoride, manganate, dimanganate, permanganate,
hypomanganate, chromate, dichromate, sulfate, sul?te,
dithionite, thiosulfate, cyanate, thiocyanate compound
or any combination thereof,
Wherein after being ?red at a ?ring temperature of above
4000 C., areas of the substrate that are exposed to the
coating composition exhibits a frosted appearance,
Wherein the temperature is chosen to be above the acti
vation temperature of the gas releasing material, above
Which the gas releasing material yields gas bubbles and
above a temperature that causes the glass frit particles to
behave as a viscous liquid.
12. The article of claim 11, Wherein upon ?ring the gas
least 4000 C., the gas releasing material comprised of
carbonate, bicarbonate, nitrate, nitrite, iodate, periodate,
bromate, perbromate, chlorate, perchlorate, ?uoride,
manganate, dimanganate, permanganate, hypomangan
ate, chromate, dichromate, sulfate, sul?te, dithionite,
thiosulfate, cyanate, thiocyanate or any combination
thereof, Wherein the composition imparts a frosted
appearance to a ceramic surface after being applied to
the ceramic surface and the ceramic surface is being
?red at a ?ring temperature of above 4000 C., at least a
portion of the substrate has a frosted appearance,
Wherein the temperature is chosen to be above the acti
vation temperature of the gas releasing material, above
Which the gas releasing material yields gas bubbles and
above a temperature that causes the glass frit particles to
behave as a viscous liquid.
releasing material releases gas bubbles of at least one of
16. The liquid of claim 15, Wherein upon ?ring the gas
carbon dioxide (CO2), Water (H2O), nitrogen oxides (NO
and/or N02), oxygen (02), nitrogen (N2), sulfur dioxide
(S02), iodine (l2) bromine (Brz), chlorine (C12), ?uorine (F2),
releasing material releases gas bubbles of at least one of
carbon monoxide (CO) and any combination thereof.
13. The article of claim 11, Wherein the ceramic substrate is
glass.
carbon dioxide (CO2), Water (H2O), nitrogen oxides (NO
and/or N02), oxygen (02), nitrogen (N2), sulfur dioxide
(S02), iodine (l2) bromine (Brz), chlorine (C12), ?uorine (F2),
carbon monoxide (CO) and any combination thereof.
*
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