Abstract: In a insert-type continuous casting nozzle comprising a highly functional layer formed to have a high corrosion resistance, a high anti-attachment capability, etc., and provided to define an inner bore thereof, the present invention is directed to providing a refractory material (mortar) for an intermediate layer of the continuous casting nozzle, which has a property capable of fixing an inner bore-side layer to an outer periphery-side layer (a nozzle body) of the continuous casting nozzle, while preventing the occurrence of expansion splitting in the outer periphery-side layer due to a difference in thermal expansion between the inner bore-side and outer periphery-side layers, and a continuous casting nozzle using the refractory material for the intermediate layer. The refractory material for the intermediate layer contains a hollow refractory aggregate in an amount of 10 to 75 volume%, wherein a ratio of an average radius R of each particle of the aggregate to an average wall thickness t of the particle satisfies the following relation: R/t > 10. This refractory material is disposed between an inner bore-side layer (2) and an outer periphery-side layer (3,4) of a continuous casting nozzle.
2 in an amount of 70
mass% or more, and an alkali metal oxide and an alkaline earth metal oxide in a total amount of
1 to 10 mass%, with the remainder (after excluding the SiC>2, the alkali metal oxide and the
alkaline earth metal oxide) being a neutral oxide and/or an acidic oxide other than SiC>2.
Specifically, the remainder is most preferably an aluminosilicate-based material comprising
A1203.
[0075]
The above composition, particularly, with the remainder being an aluminosilicate-based
material comprising AI2O3, has a softening point of 1000 to 1400°C (in the present invention, the
term "softening" means a state in which a deformation (different from breaking) occurs in an
outer shape under a pressure of 2.5 MPa or less), and facilitates softening/deformation of the
intermediate layer in a high-temperature region to increase a compressable amount under a hot
condition.
[0076]
The hollow refractory aggregate exhibits compressibility based on brittle failure by a
pressure of 2.5 MPa or less, in a low-temperature region of less than about 1000°C before
softening. Further, the hollow refractory aggregate includes the vitreous composition
containing an alkali metal oxide and an alkaline earth metal oxide in a total amount of 1 to 10
mass%. This facilitates softening/deformation of the hollow refractory aggregate in a
high-temperature range of about 1000 to 1500°C (temperature of molten steel) to allow the
hollow refractory aggregate to be reduced in volume so as to contribute to realization of a stress
absorption capability and a hot strength.
[0077]
If the amount of SiCh is less than 70 mass% and the total amount of an alkali metal oxide
and an alkaline earth metal oxide is greater than 10 mass%, or if the amount of SiC>2 is 70 mass%
or more and the total amount of an alkali metal oxide and an alkaline earth metal oxide is greater
than 10 mass%, viscosity of molten glass is likely to cause a problem in preparing a hollow raw
material, and low high-temperature viscosity is likely to cause a problem in a bonding force for
holding the inner bore-side layer. Further, if the amount of Si02 is less than 70 mass% and the
total amount of an alkali metal oxide and an alkaline earth metal oxide is less than 1 mass%, or if
the amount of SiCh is 70 mass% or more and the total amount of an alkali metal oxide and an
alkaline earth metal oxide is less than 1 mass%, the vitreous composition tends to have an
excessively high viscosity to cause a problem in preparing a hollow raw material and a problem
of deterioration in softening/deformation behavior and in adhesive force for holding the inner
bore-side layer, in a high-temperature region.
[0078]
In specifying a composition of the hollow refractory aggregate in the present invention, a
volatile material and a combustible material in a non-oxidation atmosphere are not included
therein. Specifically, the composition is specified based on a sample after a heat treatment in a
non-oxidation atmosphere at about 600°C or more.
[0079]
Before the hollow refractory aggregate is reduced in volume through softening and breaking
by stress, it exists in the refractory composition as an aggregate having a volume. Thus, the
hollow refractory aggregate allows the intermediate layer to exhibit and maintain a higher
structural strength and a higher stress distribution capability, while significantly reducing
intrusion or penetration of extraneous fluid, such as molten metal or air, as compared, for
example, with a conventional mortar initially having a void therein. Therefore, the hollow
refractory aggregate can also contribute to stability of the intermediate layer itself, stability of a
layer structure of the continuous casting nozzle, etc., as described later.
[0080]
The intermediate layer is required to have an ability to prevent displacement, peel-off,
breaking, etc., of the inner bore-side layer, even if the inner bore-side layer receives an external
force in various stages of transport, installation, preheating, and passing of molten steel of the
continuous casting nozzle.
[0081]
In a mortar having a large volume of void simply formed in a refractory matrix structure,
the structure is broken after shrinkage to cause embrittlement of the intermediate layer itself and
deterioration in bonding strength, resulting in breakup of the intermediate layer itself.
Consequently, it leads to a significant high risk of causing peel-off and breaking of the inner
bore-side layer, intrusion of molten steel, etc., between the inner bore-side and outer
periphery-side layers, etc.
[0082]
It has been found that troubles related to the inner bore-side layer during casting operation
are mostly caused by insufficiency in bonding capability of the intermediate layer. Thus, in
case where the intermediate layer is required to have a high bonding capability, it is necessary to
allow the inner bore-side layer to be stably bonded to the outer periphery-side layer during
passing of molten steel at high temperatures, while maintain a given structural strength through
the intermediate layer, particularly, after the intermediate layer is compressed by thermal
expansion of the inner bore-side layer.
[0083]
As mentioned above, the compressibility of the refractory material of the intermediate layer
of the present invention is primarily achieved by breaking/deformation of the hollow refractory
aggregate, and therefore a matrix structure has a higher strength and a higher density as
compared with the conventional mortar. Thus, deterioration in structural embrittlement
(deterioration in breaking strength) and deterioration in bonding strength are significantly
suppressed.
[0084]
Further, when a given stress is applied to the refractory structure of the intermediate layer,
only a part of the hollow refractory aggregate necessary for compressibility is broken, or the
hollow refractory aggregate is softened and deformed under a hot condition in a non-oxidation
atmosphere at a temperature of 1000 to 1500°C (temperature of molten steel), to relax the stress
to prevent breaking or the like of the continuous casting nozzle. Simultaneously, the remaining
part of the hollow refractory aggregate unnecessary for compressibility maintains a shape thereof
to serve as a backbone of the refractory material of the intermediate layer.
[0085]
During breaking or softening/deformation of the hollow refractory aggregate, only a part of
the shells of the hollow refractory aggregate particles receiving a compression stress, for
example, from a matrix portion therearound, are reduced in volume in such a manner that shell
walls of the hollow refractory aggregate particles are broken or deformed toward respective
insides of the hollow refractory aggregate particles. The hollow refractory aggregate particles
are dispersed in the matrix structure. Thus, the breaking or softening/deformation of the hollow
refractory aggregate never causes a large local deformation in the matrix structure or breaking of
the matrix structure at a level precluding a possibility to maintain shape retainability which
would otherwise occur in the conventional high-porosity mortal.
[0086]
Accordingly, the hollow refractory aggregate can exist while being in close contact with a
portion of the matrix structure therearound, i.e., without forming a void in the portion of the
matrix structure therearound, and maintaining a configuration as an aggregate in an unbroken
refractory structure. Thus, the intermediate layer can maintain a strong and dense structure
while almost preventing a formation of pores and voids in a contact surface between the inner
bore-side and outer periphery-side layers, and stably maintain bond between the inner bore-side
and outer periphery-side layers while receiving an external force by expansion of the inner
bore-side layer.
[0087]
However, it is desirable to more positively impart a bonding capability to a contact surface
between the intermediate layer and each of the inner bore-side and outer periphery-side layers.
[0088]
Therefore, in the present invention, a formation of a product, such as carbide, through a
reaction of a metal at high temperatures, is used as a means to enhance the bonding capability of
the intermediate layer. Specifically, the refractory material for the intermediate layer of the
present invention contains, as a percentage with respect to a total amount of the remainder after
excluding the hollow refractory aggregate contained in an amount of 10 to 75 volume%, one or
more (hereinafter referred to collectively as "specific metal") selected from the group consisting
of Al, Si, Mg and an alloy comprising any combination of two or more thereof, in a total amount
of 0.5 to 15 mass% in terms of only a content of the metals, and carbon in an amount of 2 to 99.5
mass%. In specifying a composition of the hollow refractory aggregate in the present
invention, a volatile material and a combustible material in a non-oxidation atmosphere are not
included therein. Specifically, the composition is specified based on a sample after a heat
treatment in a non-oxidation atmosphere at a temperature of about 600 to 800°C.
[0089]
As above, the specific metal and carbon coexist in the remainder in a dispersed manner.
This makes it possible to enhance a bonding strength of the intermediate layer and a binding
strength of the refractory structure itself under a hot condition at a temperature of about 800°C or
more, particularly about 1000°C or more, in cooperation with carbon bond derived from a resin
or the like generally for use in binding between components of a refractory material and ensuring
shape retainability.
[0090]
This function is considered as follows. Through coexistence with carbon, the specific
metal is exposed to a reduction atmosphere during casting operation. Thus, the specific metal is
vaporized as Mg-based gas and/or Al-based gas, and a part of the vaporized gas is deposited and
bonded (hereinafter referred to simply as "deposited") to pores or other portion in the refractory
structure where a partial pressure of oxygen would be relatively high, in the form of metal
carbide and/or metal oxide. The oxide of the specific metal is also deposited concentratedly on
a portion other than the pores formed inside the refractory material, such as a portion adjacent to
the refractory material, particularly, pores and voids adjacent to a contact interface between the
intermediate layer and molten steel containing oxygen components.
[0091]
A structural strength and bonding capability of the refractory material of the intermediate
layer at a temperature less than about 800°C are primarily provided by the carbon bond derived
from resin or the like. At a high temperature of about 800°C or more, particularly about 1000°C
or more, a binding structure based on a carbide created by a reaction between the specific metal
and carbon, an oxide created by the deposit, etc., is added to the carbon bond derived from resin
or the like, etc., to enhance bindability.
[0092]
In the above manner, an internal strength of the refractory structure of the intermediate layer
is enhanced, and a bonding force between the inner bore-side layer and the outer periphery-side
layer is enhanced. In addition, a significant effect of preventing intrusion/penetration of molten
steel and other foreign substances into the intermediate layer is obtained (the binding structure
based on the deposit will hereinafter be also referred to as "re-binding structure").
[0093]
In the refractory material of the present invention, even if the hollow refractory aggregate is
broken or deformed and reduced in volume, a portion of a matrix structure other than the hollow
refractory aggregate is not largely damaged. Further, even if damage occurs in a part of the
binding structure and the matrix structure, the re-binding structure is formed to contribute to
reproducing or reinforcing the binding structure for the matrix of the intermediate layer, and
enhancing the bonding strength between the inner bore-side and outer periphery-side layers.
Consequently, the bonding strength is enhanced without deterioration at a high temperature of
about 1000°C or more.
[0094]
In the present invention, the above advantageous effects of the hollow refractory aggregate,
the specific metal and the carbon are absolutely different from those of the conventional
techniques, such as a mortal-based technique, where a large volume or size of void exists from a
time before initiation of receiving of molten steel, and only binding derived from resin or the like
is exhibited in an initial stage of passing of molten steel, whereafter structural compression and
breaking are promoted.
[0095]
The bonding capability can be quantitatively expressed by bonding strength, as follows.
Preferably, with respect to each of the inner bore-side layer and the outer periphery-side layer,
the intermediate layer has a bonding strength of 0.01 to 1.5 MPa, as measured under a hot
condition in a non-oxidation atmosphere at a temperature of 1000 to 1500°C (temperature of
molten steel). As a prerequisite to having the bonding strength, it is understood that the
intermediate layer itself has a structural strength equal to or greater than the bonding strength.
Thus, the following description will be made about only the bonding strength.
[0096]
If the bonding strength is less than 0.01 MPa, an ability to holding the inner bore-side layer
becomes lower, which is likely to cause peel-off of the inner bore-side layer, due to shock at start
of passing of molten steel or a change in flow rate of molten steel, or when a local melting loss
occurs in the inner bore-side layer. If the bonding strength is greater than 1.5 MPa, a strength
of an internal structure of the intermediate layer is also increased to the same level as that of the
bonding strength to spoil compressibility of the intermediate layer. Thus, a thermal expansion
force of the inner bore-side layer is likely to be transmitted to the outer periphery-side layer
without being relaxed, and particularly likely to cause splitting or cracking of the outer
periphery-side layer.
[0097]
The bonding strength can be evaluated as a compression shear strength S. Specifically, as
shown in FIG. 2, a tubular sample having a three-layer structure in which an inner bore-side
layer 2 is provided inside an outer periphery-side layer 3(4) through an intermediate layer 1 is
placed on a table 8, and evenly heated under a given hot condition for a given holding time.
Then, a maximum load P (N) and a displacement of the inner bore-side layer are measured while
pressing only a top surface of the inner bore-side layer by a crosshead 9 moved at a speed of
0.001 to 0.1 mm/sec, and the compression shear strength S is calculated according to the
following Formula 4: S (Pa) = P / A, wherein A is a bonded area (m2) of the inner bore-side layer
to the intermediate layer.
[0098]
A shape of the sample is not particularly limited as long as it is a tubular shape. The
sample may be cut out from an actual nozzle, and subjected to the measurement. If the bonded
area A is increased, the maximum load P is also increased. Thus, a maximum height dimension
of the sample is preferably set to 100 mm. The measurement is performed at a minimum
temperature of 1000°C and in a non-oxidation atmosphere. The reason is that 1000°C
corresponds to a temperature at which a volatile material in an organic binder is sufficiently
released to complete a carbon-based binding structure so that stable compressibility and bonding
capability are exhibited, and a temperature at which the reaction to deposit of the specific metal
is initiated.
[0099]
If the content of the specific metal in the remainder is greater than 15 mass%, the structural
strength and the bonding capability of the intermediate layer are enhanced. On the other hand,
the binding structure based on the metal carbide excessively increases the strength of the
refractory structure of the intermediate layer, which is likely to spoil compressibility of the
intermediate layer to cause difficulty in obtaining required compressibility. Moreover, the
specific metal is melted during a course of temperature rise to cause a risk of flowing out from
an original position in the matrix, which is likely to cause difficulty in uniformly obtaining the
structural strength and the bonding force over the intermediate layer. This also leads to breakup
of a part of the matrix structure and formation of an interlayer gap, and molten steel and other
foreign substances are likely to intrude into a resulting void or the like. If the content of the
specific metal in the remainder is less than 0.5 mass%, the effect of enhancing the structural
strength of the intermediate layer and increasing the bonding strength in a non-oxidation
atmosphere at 1000°C to 0.01 MPa or more cannot be obtained, and segregation is likely to
occur. Moreover, this is likely to lead to breaking or peel-off of the intermediate layer and
intrusion of molten steel and other foreign substances.
[0100]
The specific metal is limited to at least one of Al, Si and Mg for the following reason. In
the specific metal, Al or Mg has a high affinity with oxygen, and an ability to capture oxygen to
form a deposit excellent in corrosion resistance, such as AI2O3 or MgO. Further, Si reacts with
carbon in the intermediate layer at a high-temperature region of about 1300°C or more to form
SiC excellent in corrosion resistance. Preferably, a purity of the specific metal is maximized in
view of reactivity and dispersibility. However, as long as the reactivity is impaired, the purity
of the specific metal may be lowered (any metal or alloy sold on the market (industrially
produced and generally distributed) with a label indicating that a primary component consists of
the specific metal).
[0101]
Preferably, a particle size of the specific metal is minimized in view of reactivity and
dispersibility. However, as the particle size becomes smaller, a handling risk becomes higher,
and oxidation in air is more likely to occur. Thus, preferably, a lower limit and an upper limit
of the particle size are set to about 5 um, and about 300 um, respectively. More preferably, the
particle size is set to 20 um or less, because, when the particle size is set to 20 um or less, a
surface area is sharply increased to provide enhanced reactivity and more enhanced
dispersibility.
[0102]
As a percentage with respect to a total amount of the remainder in the intermediate layer, a
carbon component to be reacted with the specific metal is essentially contained in an amount of
15to99.5mass%.
[0103]
A carbon source may be: a thermosetting resin, such as a phenol resin which leaves carbon
during heating-up; various types of pitches; carbon black; graphite and carbon fiber. A
combination of two or more of these materials may also be used. Preferably, the carbon source
contains: carbon having a minimized particle size, such as carbon black; or amorphous carbon
derived from the binding structure (hereinafter referred to simply as "fine carbon") to enhance
reactivity with the specific metal, and uniformity. Further, an organic adhesive or resin, such as
polyvinyl acetate-based resin, epoxy resin, acrylic resin or polyester resin, may be used in order
to impart structural strength in a temperature range of room temperature to about several hundred
°C.
[0104]
Preferably, the matrix structure of the refractory material of the intermediate layer further
contains a base material for forming a backbone of the continuous binding structure and the
matrix structure, such as graphite or carbon fiber (hereinafter referred to simply as "backbone
carbon"), in addition to the fine carbon providing fundamental structural strength and bonding
force. In particular, graphite and carbon fiber are preferable, because graphite can provide a
flexible and continuous three-dimensional structure by taking advantage of a layered crystal
structure and a flat particle shape thereof, and carbon fiber can also provide the same
three-dimensional structure.
[0105]
The flexible and continuous three-dimensional structure can be formed in the matrix in the
above manner. In this case, toughness can also be imparted to the binding structure including
carbide after reaction with the specific metal, to suppress breakup of a portion of the matrix
therearound which would otherwise occur when the hollow refractory aggregate is deformed or
broken by stress, so as to further enhance soundness as a layer.
[0106]
In regard to a specific rate of the fine carbon and the backbone carbon, the backbone
carbon, such as graphite or carbon fiber, having a large aspect ratio and an effect of enhancing
three-dimensional continuity, is contained, as a percentage with respect to the total carbon
amount of 15 to 99.5 mass%, in an amount of 70 to 95 mass%. If the content is less than 70
mass%, the three-dimensional continuity will deteriorate to cause a risk of spoiling flexibility.
If the content is greater than 95 mass%, the bonding strength is limited to a low level to cause a
risk of the occurrence of local breaking.
[0107]
As a method of assistively accelerating the enhancement in corrosion resistance by the
effect of the deposit of the specific metal on an operation surface based on the coexistence of the
specific metal and carbon, there is a technique of incorporating a refractory raw material
excellent in corrosion resistance as a component of the remainder in combination. However, in
the case where a refractory raw material consisting of a component other than the hollow
refractory aggregate is contained in a part of the remainder other than the specific metal and
carbon (the refractory raw material will hereinafter be also referred to as "additional
component"), it is necessary to select, as an additional component, a refractory aggregate
comprising a primary component free of a low-temperature melting phenomenon and a
volatilization/vanishment phenomenon at a casting temperature in relation to the inner bore-side
layer and the outer periphery-side layer. If a liquid phase is created at the casting temperature
due to contact with the inner bore-side layer and the outer periphery-side layer, the bonding
strength in a hot condition will be undesirably reduced, and the structural strength of the
refractory material of the intermediate layer will be undesirably increased to a level spoiling
compressibility, for example, due to excessive sintering. The inside of the refractory material
of the intermediate layer is exposed to a strong reduction atmosphere. Thus, if the additional
component is a highly volatile component, such as a SiC>2 component, which is not formed as a
mineral substance, the additional component itself will be undesirably vaporized and vanished,
while causing vanishment of a carbon component.
[0108]
An aggregate selectable for the additional component includes AI2O3, MgO, Z1O2 and
AI2O3 • MgO-based spinel. The additional component may be appropriately selected from these
components in conformity to a material of the inner bore-side layer to prevent a contact portion
between the intermediate layer and the inner bore-side layer from creating a low-melting-point
substance or the like. For example, when the inner bore-side layer consists of a CaO-containing
refractory material, an MgO-based refractory aggregate is suitable. When the inner bore-side
layer primarily comprises an AI2O3 or MgO-based material, AI2O3, MgO or AI2O3 • MgO-based
spinel is suitable. Preferably, the additional component comprises an MgO-based refractory
aggregate containing MgO at a purity of 90% or more. In this case, the additional component is
suitable when the inner bore-side layer consists of an Al203-based material or a Zr02-based
material, and desirably capable of widely coping with various inner bore-side layers.
[0109]
In case where a lower limit of a thickness of the intermediate layer is set to 1 mm, a particle
size of the refractory aggregate constituting the additional component is preferably set to 0.5 mm
or less to enhance dispersibility, and uniformity in the aforementioned various functions of the
intermediate layer.
[0110]
The intermediate layer is required to have corrosion resistance in such a case that, when a
deficient portion is formed in the inner bore-side layer due to various actions during casting
operation, it is necessary to suppress or prevent molten steel and other foreign substances from
being brought into direct contact with the outer periphery-side layer having lower corrosion
resistance, and it is necessary for the intermediate layer itself to reliably have durability, such as
corrosion resistance and erosion resistance.
[0111]
In the continuous casting nozzle, a portion to be directly exposed to molten steel, such as a
deficient portion of the inner bore-side layer due to damage, a locally damaged portion in a weak
region (e.g., an interface region between the inner bore-side layer and the nozzle body (outer
periphery-side layer), a gas pool for gas injection or an interlayer junction), such as an interface
region between the inner bore-side layer and the nozzle body (outer periphery-side layer), or an
outlet portion of an immersion nozzle, exists or is likely to exist even in the form of a workpiece
during a course of a production process thereof or a unused product. If the portion to be
directly exposed to molten steel is poor in durability, such as corrosion resistance and erosion
resistance, molten steel will intrude between the inner bore-side and outer periphery-side layers,
for example, due to a selective vanishment of the portion, to case a defect of the continuous
casting nozzle fatal to continuous casting operation, such as breaking of the continuous casting
nozzle.
[0112]
The refractory material for the intermediate layer of the present invention is suitable for a
continuous casting nozzle having a function or structure for allowing molten steel to pass
through an inner bore thereof, such as an immersion nozzle, an open nozzle, a long nozzle for a
ladle, a sliding nozzle (hereinafter referred to as "SN"), an SN upper nozzle, or an SN lower
nozzle (also called "collector").
[0113]
A material for the inner bore-side layer of the continuous casting nozzle is not limited to a
specific type, but a refractory material, such as an Al203-based material, an MgO-based material
or a Zr02-based material, having properties required for the continuous casting nozzle depending
on each continuous casting operation, specifically, such as erosion (abrasion) resistance of a
portion for contact with molten metal, corrosion resistance of an inner bore, anti-attachment of
inclusions such as AI2O3, onto an inner bore, and suitable for each intended purpose, may be
used on a case-by-case basis (the refractory material may contain graphite and other component).
Similarly, a material for the outer periphery-side layer of the continuous casting nozzle is not
limited to a specific type. The outer periphery-side layer typically serves as a nozzle body of
the continuous casting nozzle. Thus, a part or entirety of a portion of the outer periphery-side
layer may be made of a refractory material, such as a conventional AbOs-graphite based
material, and a part or entirety of the mold-power portion may be made of a refractory material,
such as a ZrCVbased material.
[0114]
The refractory material for the intermediate layer of the present invention is suitably used,
particularly, in a combination of inner bore-side and outer periphery-side layers, wherein a
refractory material of the inner bore-side layer has a thermal expansion coefficient greater than
that of a refractory material of the outer periphery-side layer. It is understood that the
refractory material for the intermediate layer of the present invention may also be used in case
where, although each of inner bore-side and outer periphery-side layers has the same thermal
expansion coefficient, for example, because they are made of the same material, a temperature
gradient in a continuous casting nozzle formed by the inner bore-side and outer periphery-side
layers or thermal shock to be supplied to the continuous casting nozzle is large enough to cause
breaking of the continuous casting nozzle.
[0115]
Based on the above knowledge about the intermediate layer, the inventors have further
found that a unique condition exists when a CaO-MgO based refractory material is provided as
an inner bore-side layer.
[0116]
As disclosed, for example, in JP 2003-320444A, a CaO-MgO based refractory material is
provided as an inner bore-side layer of a continuous casting nozzle to allow conventional
problems, particularly, a problem of attachment of inclusions (typically, alumina) onto a surface
of an inner bore and clogging of the inner bore, to be solved. However, the technique of
employing the CaO-MgO based refractory material as an inner bore-side layer gave rise to new
problems, particularly, a problem of breaking of an outer periphery-side layer due to expansion
splitting, melting loss, breaking or peel-off of the inner bore-side layer, intrusion of scull
between the inner bore-side layer and the outer periphery-side layer, or breaking of various
regions of the nozzle.
[0117]
Therefore, in the present invention, for the continuous casting nozzle where the inner
bore-side layer is made of an MgO-CaO based refractory material, measures are taken to prevent
damage of the outer periphery-side layer due to thermal expansion of the inner bore-side layer,
and maintain fixation with each of the inner bore-side layer and the outer periphery-side layer
without formation of a void space between the inner bore-side and outer periphery-side layers
causing intrusion of molten metal.
[0118]
Firstly, in the present invention, a composition of a CaO-MgO based material to be
provided as an inner bore-side layer is specified. Specifically, a CaO-MgO based material
containing a CaO component and an MgO component in a total amount of 80 mass% or more,
wherein a mass ratio of CaO to MgO (CaO/MgO) is in the range of 0.2 to 1.5, is provided as an
inner bore-side layer.
[0119]
Thus, the inner bore-side layer having a CaO component-based function of maintaining
attachment resistance and an MgO component-based function of maintaining corrosion
resistance in a balanced manner is provided to sufficiently bring out an anti-alumina clogging
function.
[0120]
The CaO component reacts with an in-steel alumina-based deoxidation product which
comes on a molten steel stream and into contact with a surface of an inner bore of the continuous
casting nozzle, to create a CaO-AkOa based low-melting-point substance on a contact interface.
This allows a slagged reaction product to easily flow down into a mold on the molten steel
stream so as to prevent an alumina-clogging phenomenon in the nozzle. On the other hand,
when an amount of the CaO component is increased, the CaO component will be continuously
supplied from the refractory material to molten steel, so that an amount of melting loss in the
refractory material is increased, and an amount of inclusions in steel is increased to cause
deterioration in steel quality.
[0121]
Although the MgO component is advantageous in terms of melting-loss resistance, because
it does not create any low-melting-point substance through a reaction with an alumina
component, an increase in amount of the MgO component is disadvantageous in terms of the
alumina-clogging phenomenon.
[0122]
Thus, the mass ratio CaO/MgO and the total amount (CaO + MgO) are critical parameters
having an impact on melting-loss resistance and alumina-attachment resistance. Further, in
terms of continuous casting operation, a flow rate of molten steel and an amount of alumina
contained in molten steel have an impact on the melting-loss resistance and the
alumina-attachment resistance. Generally, as the molten-steel flow rate becomes higher, an
amount of alumina attachment becomes smaller and an amount of melting loss becomes larger.
Further, as a concentration of in-steel alumina becomes higher, alumina attachment is
accelerated under a certain condition. In conclusion, it is necessary to perform a material
design in a composition range capable of achieving a balance between the alumina-attachment
resistance and the melting-loss resistance while taking into account the conditions of casting
operation and the type of molten steel.
[0123]
In accordance with the above requirements, in the present invention, the composition of the
inner bore-side layer is specified as described above. Specifically, if the mass ratio of the CaO
component to the MgO component (CaO/MgO) is less than 0.2, the CaO component cannot be
continuously supplied from the inner bore-side layer under typical conditions of casting
operation where the molten-steel flow rate is 5t/min or less, which precludes a possibility to
maintain the alumina-attachment resistance. If the mass ratio CaO/MgO is greater than 1.5, the
supply of the CaO component from the inner bore-side layer will be excessively increased to
cause an increase in amount of melting loss in the inner bore-side layer itself, and an increase in
amount of in-steel inclusions. The total amount of the CaO component and the MgO
component is set to 80 mass% or more so as to achieve a balance between corrosion resistance
and melting-loss resistance.
[0124]
Preferably, the remainder after excluding the CaO component and the MgO component is
comprised of a refractory material other than the CaO component and the MgO component,
particularly, a carbon-based refractory material, in view of maintaining a balance between the
corrosion resistance and the melting-loss resistance (anti-attachment). In the case where a
carbon-based refractory material is used as the reminder, if the total amount of the CaO
component and the MgO component is less than 80 mass%, an amount of a carbon component in
the reminder is excessively increased, and thereby melting of the carbon component into molten
steel becomes prominent to cause a problem that an amount of melting loss in the inner bore-side
layer is excessively increased to shorten a lifetime of the nozzle, and an amount of in-steel
inclusions is increased.
[0125]
A CaO component source and an MgO component source to be used in the refractory
material of the inner bore-side layer may be a dolomite clinker, a synthetic dolomite raw
material, a magnesia raw material, or a calcia raw material. In particular, a CaO component in
a burnt dolomite clinker continuously exists in the clinker. Thus, the burnt dolomite clinker is
desirable in terms of continuous supply of CaO.
[0126]
Preferably, a particle size of the CaO and MgO components is set in the range of 0.1 to 3
mm. If the particle size is less than 0.1 mm, a hydration phenomenon is likely to occur to cause
problems in quality stability and volume stability, for example, in case where an
MgO-CaO-based fine power is used in a large amount. If the particle size is greater than 3 mm,
nonuniformity in composition or particle size in a shaped body is likely to occur, which is
undesirable in terms of uniformity.
[0127]
An intermediate layer for use with the above inner bore-side layer made of a CaO-MgO
based material is prepared in such a manner that, after a heat treatment in a non-oxidation
atmosphere at a temperature of about 600°C, it contains a hollow refractory aggregate in an
amount of 10 to 75 volume%, with the remainder which contains, on an assumption that a total
amount of the remainder is 100 mass%, one or more selected from the group consisting of Al, Si,
Mg and an alloy comprising any combination of two or more thereof, in a total amount of 0.5 to
15 mass% in terms of only a content of the metals, and carbon in an amount of 2 to 99.5 mass%,
wherein a value derived by dividing a mass ratio of CaO contained in the inner bore-side layer to
the entire inner bore-side layer by a mass ratio of a total of AI2O3, SiC>2 and an alkali metal oxide
contained in the intermediate layer to the entire intermediate layer is 10 or more, as mentioned
above.
[0128]
The reason is as follows. If the CaO component in the inner bore-side layer which
contains the CaO component and the MgO component in a total amount 80 mass% or more,
wherein the mass ratio of CaO to MgO (CaO/MgO) is in the range of 0.2 to 1.5, comes into
contact with a large amount of AI2O3 and Si02 components, a CaO-Al203-Si02 based reaction
product will be created, particularly, in prolonged casting operation, wherein the CaO component
in the inner bore-side layer is consumed during the reaction, so that a function of capturing an
AI2O3 inclusion in molten steel is lowered, and a bonded portion with the intermediate layer is
excessively strengthened and deformed with shrinkage or the like to produce an uneven tension
stress in the inner bore-side layer to increase a possibility to give rise to breaking (cracking) in
the inner bore-side layer.
[0129]
When an alkali metal oxide is added to the Al2O3-SiO2 based component, the above
phenomenon is accelerated. Further, if the value derived by dividing a mass ratio of CaO
contained in the inner bore-side layer to the entire inner bore-side layer by a mass ratio of a total
of AI2O3, SiO2 and an alkali metal oxide contained in the intermediate layer to the entire
intermediate layer is less than 10, the phenomenon becomes prominent.
[0130]
In view of providing enhanced corrosion resistance against molten steel to an intermediate
layer for use with the inner bore-side layer made of a CaO-MgO based material, an MgO-based
refractory aggregate or an AI2O3 • MgO-based spinel refractory aggregate is suitably used as
refractory aggregate particles as the remaining component of the intermediate layer after
excluding the hollow refractory aggregate, the carbon and the specific metal. Preferably, an
amount of the MgO-based refractory aggregate or the AI2O3 • MgO-based spinel refractory
aggregate to be contained in the remaining component is adjusted to be 50 mass% or more
(including 100 mass%).
[0131]
A first reason is to provide a material combination which is less likely to produce an
excessive cross-reaction, such as sintering or melting, in an interface between the inner bore-side
and outer periphery-side layers. For the inner bore-side layer which contains the CaO
component and the MgO component in a total amount 80 mass% or more, wherein the mass ratio
of CaO to MgO (CaO/MgO) is in the range of 0.2 to 1.5, a magnesia or spinel (spinel comprising
AI2O3 and MgO) based refractory aggregate itself or a mixture comprising the refractory
aggregate is optimal, because it is less likely to produce a cross-reaction with the above
refractory material of the inner bore-side layer.
[0132]
A second reason is that the MgO-based refractory aggregate or the AI2O3 • MgO-based
spinel refractory aggregate is less likely to produce a cross-reaction with an Al203-Si02-C,
AI2O3-C, Zr02-C or MgO-C based refractory material commonly used as an outer periphery-side
layer.
[0133]
A third reason is that, as compared with other aggregate, such as alumina-silica based
refractory aggregate particles, MgO is relatively less likely to produce a cross-reaction with a
vitreous component, a silica component, etc., in the hollow refractory aggregate.
[0134]
In the above case, the outer periphery-side layer (nozzle body) may be made of any one of
an Al203-C-based refractory material, a ZrCh-C-based refractory material and an MgO-C-based
refractory material, wherein a relationship between C and each of AI2O3, Z1O2 and MgO, such as
a composition ratio and an existence form, is not particularly limited.
EFFECT OF THE INVENTION
[0135]
As above, in a continuous casting nozzle, when an inner bore-side region has thermal
expansion greater than that of an outer periphery-side region, and, particularly, when a
highly-functional layer having high corrosion resistance, high attachment resistance, etc., is
disposed on the side of an inner bore to enhance durability, the refractory material of the present
invention is used for an intermediate layer of the continuous casting nozzle. This makes it
possible to prevent expansion splitting of an outer periphery-side layer due to a difference in
thermal expansion between an inner bore-side layer, and the outer periphery-side layer as a
nozzle body, and prevent peel-off and breaking of the inner bore-side layer during casting
operation.
[0136]
In addition, based on a deposit of the specific material, a stable bonding capability can be
obtained, while achieving higher density and higher structural strength of the refractory material
itself of the intermediate layer, so as to improve stability of a multi-layer structure and corrosion
resistance of the intermediate layer.
[0137]
Furthermore, the present invention provides an inner bore-side layer having a significantly
high effect of suppressing attachment of inclusions (typically, AI2O3) onto the inner bore.
Further, in the use of such an inner bore-side layer, the present invention makes it possible to
prevent the occurrence of excessively strong bonding between the inner bore-side layer and the
intermediate layer due to a CaO component, and solve a problem causing breaking (cracking) of
the inner bore-side layer, such as drop-off or displacement of the inner bore-side layer due to
insufficient bonding, to allow continuous casting operation to be stably performed over a long
period of time.
[0138]
In the continuous casting nozzle of the present invention, various refractory materials
having properties required for the continuous casting nozzle depending on unique conditions of
each continuous casting operation, specifically, such as erosion (abrasion) resistance of a portion
for contact with molten metal, corrosion resistance of an inner bore, anti-attachment of
inclusions such as AI2O3, onto an inner bore, and suitable for each intended purpose, can be used
for each region on a case-by-case basis, so that the number of selectable materials and
combinations thereof can be significantly increased. This also contributes to extension of a
lifetime of a continuous casting nozzle, enhancement of steel quality, stable casting operation,
and resource saving.
1
BRIEF DESCRIPTION OF THE DRAWINGS
[0139]
FIG. 1 is a sectional view of an immersion nozzle as one example of a continuous casting
nozzle using a refractory material for an intermediate layer of the present invention, taken along
an axis thereof.
FIG. 2 is a schematic sectional view showing a sample and a testing apparatus during a
bonding strength test, taking along an axis of the sample.
FIG. 3 is a schematic vertical sectional view showing a sample and a testing apparatus
during a breaking test for a hollow refractory aggregate in Example A.
BEST MODE FOR CARRYING OUT THE INVENTION
[0140]
A method of producing a refractory material of the present invention will be firstly
described.
In case where the refractory material itself of the present invention comprises a hollow
refractory aggregate, carbon, and a specific metal, refractory aggregate particles constituting
these components are mixed together. Then, a binder, such as an organic resin (e.g., phenol
resin or vinyl acetate resin) which is capable of wetting the obtained power mixture to provide
aggregability of the respective particles or bonding capability, and, after curing, exhibiting
structural strength enough to ensure shape retainability as a shaped body, is added to the powder
mixture in an appropriate amount required for shaping and shape retention, and they are kneaded
to obtain a kneaded mixture. Then, the kneaded mixture is filled in a pre-defined space by an
appropriate technique, such as pouring or injection, and shaped. Subsequently, the obtained
shaped body is subjected to a heating treatment, such as drying or burning, at a temperature of
about 110 to 600°C, at an appropriate temperature depending on properties of the binder and
others to obtain the refractory material. Details of the method will be described below.
[0141]
10 to 75 volume% of hollow refractory aggregate is mixed with 25 to 90 volume% of
carbonaceous particles derived from flaky graphite, amorphous or earthy graphite, carbon black,
pitch, resin or the like, and oxide particles or metal particles, such as magnesia, zirconia or
corundum-based particles.
[0142]
The 25 to 90 volume% of carbonaceous particles derived from flaky graphite, amorphous or
earthy graphite, carbon black, pitch, resin or the like, and oxide particles or metal particles, are
combined and mixed together, in such a manner that the obtained mixture comprises, as a
percentage with respect to a total amount of the remainder after excluding the hollow refractory
aggregate, one or more (specific metal) selected from the group consisting of Al, Si, Mg and an
alloy comprising any combination of two or more thereof, in a total amount of 0.5 to 15 mass%
in terms of only a content of the metals, and carbon in an amount of 2 to 99.5 mass%, with the
remainder (including zero) being a refractory aggregate other than the specific metal and carbon.
Preferably, a maximum particle size of this raw material is set to 0.5 mm or less to allow the
refractory material of the intermediate layer to have uniform compressibility while being formed
in mortar form excellent in working efficiency during application.
[0143]
An amount of the hollow refractory aggregate may be determined by calculating a required
compressive rate from a relationship between a thickness of the refractory material of the
intermediate layer and each of thermal expansion coefficients of an inner bore-side layer and an
outer periphery-side layer, and adjusting a ratio between the hollow refractory aggregate and the
remaining raw materials.
[0144]
Further, a mixing rate of each of the hollow refractory aggregate and the remaining raw
materials, i.e., the remainder such as the refractory aggregate may be adjusted in such a manner
that a value derived by dividing a mass ratio of CaO contained in the inner bore-side layer to be
combined with the intermediate layer, to the entire inner bore-side layer, by a mass ratio of a
total of AI2O3, SiCh and an alkali metal oxide contained in the intermediate layer to the entire
intermediate layer is set to 10 or more.
[0145]
Then, a binder, such as an organic resin (e.g., phenol resin or vinyl acetate resin) which is
capable of wetting the mixture to provide aggregability of the respective particles or bonding
capability, and, after curing, exhibiting structural strength enough to ensure shape retainability as
a shaped body, is added to the above powder mixture in an amount adjusted to provide softness
suitable for shaping of the mixture, and they are kneaded using a mixer, such as a mortar mixer,
to obtain a mortar mixture. On an assumption that the powder mixture is 100 mass parts, an
amount of phenol resin or other organic resin to be used may be adjusted in the range of 40 to 90
mass parts depending on required working efficiency.
[0146]
Then, the mortar mixture is filled in a space pre-defined between the inner bore-side and
outer periphery-side layers, by applying the mortar mixture onto one or both of surfaces of the
inner bore-side and outer periphery-side layers and fitting the inner bore-side layer into the outer
periphery-side layer, or other appropriate technique, such pouring or spraying, to integrate the
inner bore-side layer and the outer periphery-side layer together. Then, the filled mortar
mixture is subjected to a heating treatment, such as drying or burning, at a temperature of about
110 to 600°C, depending on properties of the binder and others, to allow the mortar mixture to
exhibit shape retainability and interlayer fixing capability.
[0147]
Practically, the above process for the refractory material of the intermediate layer is mostly
incorporated as a part of an after-mentioned production process for a continuous casting nozzle
structure to provide a continuous casting nozzle in the form of a single piece of product.
Alternatively, the refractory material may be formed as a member having any suitable shape,
such as a tubular shape, and be assembled as a part of a continuous casting nozzle. In this case,
the mortal mixture may be shaped using a mold form, and dried or burned in a non-oxidation
atmosphere to form the refractory member.
[0148]
A production method for a continuous casting nozzle using the above refractory material of
the intermediate layer will be described below.
[0149]
An inner bore-side layer is formed as a single piece of refractory shaped body, separately
from a nozzle body of a continuous casting nozzle. As long as this inner bore-side layer is
prepared as a refractory shaped body in advance, a production method therefor is not particularly
limited. A specific example will be described below, wherein the inner bore-side layer contains
a CaO component and an MgO component.
[0150]
A content rate of each component in a refractory raw material containing a CaO component
and an MgO component, such as a fine powder raw material of burnt dolomite and a fine powder
raw material of MgO clinker is adjusted in such a manner that, after a refractory shaped body of
the refractory raw material is subjected to a heat treatment in a non-oxidation atmosphere at
600°C, the refractory shaped body contains a CaO composition and an MgO composition in a
total amount of 80 mass% or more, wherein a mass ratio of CaO to MgO (CaO/MgO) is in the
range of 0.2 to 1.5. Then, a binder, such as phenol resin, which has a binding capability after a
heat treatment in a non-oxidation atmosphere at 600°C, and a liquid shaping assistant for
obtaining a wet state suitable for shaping (if the binder is in liquid form, it can also serve as the
shaping assistant) is added to the fine powder raw materials, and they are uniformly mixed
together by a mixer to obtained a mixture for shaping.
[0151]
The obtained mixture is shaped by an appropriate forming machine, such as a CIP (Cold
Isostatic Press) machine, a hydraulic press machine or a friction press machine, and the obtained
shaped body is dried at a temperature of about 150°C or more, or subjected to a heat treatment in
a non-oxidation atmosphere. Subsequently, according to need, the shaped body, such as an
outer peripheral surface thereof, is machined into a shape suitable for being attached to the
nozzle body prepared as a separate body, by a conventional machining technique. A generally
required treatment for the raw materials or the shaped body, such as measures against hydration,
may be performed depending on the raw materials and production conditions on a case-by-case
basis.
[0152]
A space having a given thickness for the intermediate layer is pre-defined between the
shaped body separately prepared as the inner bore-side layer in the above manner and the nozzle
body separately prepared as the outer periphery-side layer, and the refractory material of the
present invention is filled into the space to form the intermediate layer so as to complete a
continuous casting nozzle having a multi-layer structure.
[0153]
The refractory material of the present invention to be used for the intermediate layer is
formed in muddy unshaped form enough to be able to be filled into a narrow space between the
inner bore-side and outer periphery-side layers. With a view to providing working efficiency
during filling, a liquid resin may be added to the refractory material in an amount of about 40 to
90 mass parts (this amount is determined in consideration of a volume of the space and working
efficiency during setup) with respect to and in addition to 100 mass parts of the powder mixture
comprising the hollow refractory aggregate, the carbon raw material in solid form, and the
remaining components including the refractory aggregate, and they are kneaded.
[0154]
The refractory material for the intermediate layer improved in working efficiency during
setup is applied onto an outer peripheral surface of the inner bore-side layer provided with a
spacer for defining a given space having a thickness of the intermediate layer, or an inner
peripheral surface of the outer periphery-side layer, and then the inner bore-side layer is inserted
into the outer periphery-side layer (nozzle body of a continuous casting nozzle to be produced).
In this state, a space defined between the outer peripheral surface of the inner bore-side layer and
the inner peripheral surface of the outer periphery-side layer becomes equal to the thickness of
the intermediate layer.
[0155]
In place of the above filling technique based on application, the refractory material for the
intermediate layer may be prepared to have a higher fluidity, for example, by adding liquid at a
higher rate, and poured into a given space defined between the inner bore-side and outer
periphery-side layers.
[0156]
An obtained continuous casting nozzle having the filled refractory material for the
intermediate layer is subjected to a heating treatment, such as drying or burning, to cure the
refractory material for the intermediate layer so as to fix the inner bore-side layer to the outer
periphery-side layer. The curing may be performed at an appropriate temperature, in a
temperature range of room temperature to about 600°C, depending on properties of the binder
contained in the refractory material of the intermediate layer. For example, in case where a
vinyl-based resin is used as the binder, the curing may be achieved by drying at about 150°C.
In case where a phenol resin is used as the binder, a heating temperature is preferably set at
200°C or more. Subsequently, the continuous casting nozzle may further be burnt, for example,
in a non-oxidation atmosphere at a temperature of about 1000 to 1300°C. In the above manner,
a semifinished product of the continuous casting nozzle of the present invention can be obtained.
[0157]
The hollow refractory aggregate used in the refractory material for the intermediate layer is
kept from broking by an external force during installation/setup of the inner bore-side layer to
the outer periphery-side layer, to prevent the occurrence of an undesirable situation where a
thickness of the intermediate layer becomes excessively reduced due to the setup operation, or a
required compressibility of the intermediate layer is spoiled due to absorption of a solvent.
Further, the hollow refractory aggregate is formed in a balloon-like configuration which has a
rounded outer shape almost without an edge as in a spalled particle. This makes it possible to
obtain an advantage of being able to improve fluidity of the muddy refractory material of the
intermediate layer, i.e., to reduce an amount of liquid phase so as to achieve a dense matrix
structure.
[0158]
However, in either technique, if the hollow refractory aggregate is pressed by a pressure
greater than the structural strength thereof during shaping or setup operation, it will be broken to
lose a stress relaxation capability. Thus, the hollow refractory aggregate cannot be subjected to
various high-pressure press forming process commonly used for simultaneously/integrally
forming a plurality of layers of a continuous casting nozzle, such as cold isostatic press (OP),
based on a pressure fairly greater than at least 2.5 MPa at which the hollow refractory aggregate
is broken.
[0159]
In the above production method, a binder is used in the refractory material for the
intermediate layer to provide a shape retainability of the intermediate layer itself and a structural
strength of the intermediate layer between room temperature to a hot condition during use, and
ensure a formability of the mixture. In case where the inner bore-side layer contains an
MgO-CaO based component, particularly CaO existing by itself (not in the form of a solid
solution or a compound), it is necessary to use a binder which is devoid of water, and less likely
to release moisture during heating, in order to prevent breakup or the like of the inner bore-side
layer after setup, due to hydration of a CaO component therein. A binder meeting this
requirement includes non-water based phenol resin, non-water based furan resin, tar, melamine
resin, epoxy resin, and polyvinyl acetate resin using alcohol as a solvent.
[0160]
Carbon derived from the binder and left at 600°C or more serves as a part of a carbon
component of the refractory material of the intermediate layer.
[0161]
The semifinished product of the continuous casting nozzle after the filling and the heating
treatment may be subjected to the same process as that for conventional continuous casting
nozzle, such as machining of an outer periphery thereof and others, and application of an
antioxidant.
[0162]
Through the above production method, the continuous casting nozzle of the present
invention comprising the intermediate layer with compressibility and the inner bore-side and
outer periphery-side layers continuously integrated with the intermediate layer can be obtained.
[0163]
FIG. 1 shows an immersion nozzle as one example of the continuous casting nozzle of the
present invention. In FIG. 1, the reference numerals 1, 2, 3 and 4 indicate an intermediate
layer, an inner bore-side layer made of an MgO-CaO-based refractory material, an
alumina-graphite layer as a part of an outer periphery-side layer serving as a nozzle body of the
continuous casting nozzle, and a zirconia-graphite based layer serving as a powder region which
is remaining part of the outer periphery-side layer, respectively. Further, the reference
numerals 5,6 and 7 indicate an inner bore, a molten-steel inlet opening, and an outlet opening.
[EXAMPLE]
[0164]
Various examples will be described below.
[0165]
«
Example D is a result of a test for checking an influence of a percentage of carbon with
respect to the remainder after excluding a hollow refractory aggregate, on a compressibility and a
bonding strength, and a result of a simulation test for casting of molten steel based on inner-bore
heating.
[0189]
Table 4 shows a composition and a test result of each sample in Example D.
[0190]
A hollow refractory aggregate used in Example D has the same composition and the same
particle-size distribution as those of the hollow refractory aggregate used in each of Examples B
andC.
[0191]
In Example D, fundamentally, (except the sample containing carbon in an amount of 99.5
mass% or more), an amount of a specific metal and a phenol resin solution (converted to C to be
left after a heat treatment in a non-oxidation treatment at 1000°C) was fixed, and an amount of
carbon was changed by replacing an MgO fine powder (MgO purity: 95 to 98 mass%; other
Examples have the same condition) with a graphite fine powder.
[0192]
The measurement of a compressive rate, and a bonding strength, and the simulation test for
casting of molten steel based on inner-bore heating, were carried out in the same manner as that
in each of Examples B and C.
[0193]
As is evident from the measurement result shown in Table 4, the desired range of the
bonding strength of 0.01 to 1.5 MPa can be obtained, when a content of carbon in the remainder
metal is in the range of 2 to 99.5 mass%.
[0194]
In the inner-bore heating test, a desired result was obtained when the content of carbon is in
the range of 2 to 99.5 mass%, and this tendency primarily corresponds to the given range of the
bonding strength, as with Example C.
[0195]
| # | Name | Date |
|---|---|---|
| 1 | 617-KOLNP-2011-RELEVANT DOCUMENTS [30-08-2023(online)].pdf | 2023-08-30 |
| 1 | 617-kolnp-2011-specification.pdf | 2011-10-06 |
| 2 | 617-kolnp-2011-pct priority document notification.pdf | 2011-10-06 |
| 2 | 617-KOLNP-2011-RELEVANT DOCUMENTS [23-09-2022(online)].pdf | 2022-09-23 |
| 3 | 617-KOLNP-2011-RELEVANT DOCUMENTS [26-07-2021(online)].pdf | 2021-07-26 |
| 3 | 617-KOLNP-2011-PA.pdf | 2011-10-06 |
| 4 | 617-kolnp-2011-others pct form.pdf | 2011-10-06 |
| 4 | 617-KOLNP-2011-FORM 4 [25-02-2020(online)].pdf | 2020-02-25 |
| 5 | 617-KOLNP-2011-RELEVANT DOCUMENTS [20-02-2020(online)].pdf | 2020-02-20 |
| 5 | 617-kolnp-2011-international search report.pdf | 2011-10-06 |
| 6 | 617-KOLNP-2011-IntimationOfGrant06-11-2019.pdf | 2019-11-06 |
| 6 | 617-kolnp-2011-international publication.pdf | 2011-10-06 |
| 7 | 617-KOLNP-2011-PatentCertificate06-11-2019.pdf | 2019-11-06 |
| 7 | 617-kolnp-2011-form-5.pdf | 2011-10-06 |
| 8 | 617-KOLNP-2011-PETITION UNDER RULE 137 [05-11-2019(online)]-1.pdf | 2019-11-05 |
| 8 | 617-kolnp-2011-form-3.pdf | 2011-10-06 |
| 9 | 617-kolnp-2011-form-2.pdf | 2011-10-06 |
| 9 | 617-KOLNP-2011-PETITION UNDER RULE 137 [05-11-2019(online)].pdf | 2019-11-05 |
| 10 | 617-kolnp-2011-form-1.pdf | 2011-10-06 |
| 10 | 617-KOLNP-2011-Written submissions and relevant documents (MANDATORY) [05-11-2019(online)].pdf | 2019-11-05 |
| 11 | 617-KOLNP-2011-Annexure (Optional) [25-07-2019(online)].pdf | 2019-07-25 |
| 11 | 617-KOLNP-2011-FORM 18.pdf | 2011-10-06 |
| 12 | 617-kolnp-2011-drawings.pdf | 2011-10-06 |
| 12 | 617-KOLNP-2011-Further evidence (MANDATORY) [25-07-2019(online)].pdf | 2019-07-25 |
| 13 | 617-kolnp-2011-description (complete).pdf | 2011-10-06 |
| 13 | 617-KOLNP-2011-FORM 13 [19-06-2019(online)].pdf | 2019-06-19 |
| 14 | 617-kolnp-2011-correspondence.pdf | 2011-10-06 |
| 14 | Petition Under Rule 137 [04-04-2017(online)].pdf | 2017-04-04 |
| 15 | 617-KOLNP-2011-CORRESPONDENCE 1.1.pdf | 2011-10-06 |
| 15 | Petition Under Rule 137 [04-04-2017(online)].pdf_465.pdf | 2017-04-04 |
| 16 | 617-kolnp-2011-claims.pdf | 2011-10-06 |
| 16 | Claims [03-04-2017(online)].pdf | 2017-04-03 |
| 17 | Correspondence [03-04-2017(online)].pdf | 2017-04-03 |
| 17 | 617-kolnp-2011-abstract.pdf | 2011-10-06 |
| 18 | 617-KOLNP-2011-(05-09-2013)-PA.pdf | 2013-09-05 |
| 18 | Description(Complete) [03-04-2017(online)].pdf | 2017-04-03 |
| 19 | 617-KOLNP-2011-(05-09-2013)-OTHERS.pdf | 2013-09-05 |
| 19 | Description(Complete) [03-04-2017(online)].pdf_137.pdf | 2017-04-03 |
| 20 | 617-KOLNP-2011-(05-09-2013)-FORM-6.pdf | 2013-09-05 |
| 20 | Examination Report Reply Recieved [03-04-2017(online)].pdf | 2017-04-03 |
| 21 | 617-KOLNP-2011-(05-09-2013)-FORM-5.pdf | 2013-09-05 |
| 21 | Other Document [03-04-2017(online)].pdf | 2017-04-03 |
| 22 | 617-KOLNP-2011-(05-09-2013)-FORM-3.pdf | 2013-09-05 |
| 22 | Other Patent Document [23-01-2017(online)].pdf | 2017-01-23 |
| 23 | 617-KOLNP-2011-(05-09-2013)-FORM-2.pdf | 2013-09-05 |
| 23 | 617-KOLNP-2011-FER.pdf | 2016-10-19 |
| 24 | 617-KOLNP-2011-(05-09-2013)-FORM-13.pdf | 2013-09-05 |
| 24 | 617-KOLNP-2011-(05-09-2013)-ASSIGNMENT.pdf | 2013-09-05 |
| 25 | 617-KOLNP-2011-(05-09-2013)-CORRESPONDENCE.pdf | 2013-09-05 |
| 25 | 617-KOLNP-2011-(05-09-2013)-FORM-1.pdf | 2013-09-05 |
| 26 | 617-KOLNP-2011-(05-09-2013)-CORRESPONDENCE.pdf | 2013-09-05 |
| 26 | 617-KOLNP-2011-(05-09-2013)-FORM-1.pdf | 2013-09-05 |
| 27 | 617-KOLNP-2011-(05-09-2013)-ASSIGNMENT.pdf | 2013-09-05 |
| 27 | 617-KOLNP-2011-(05-09-2013)-FORM-13.pdf | 2013-09-05 |
| 28 | 617-KOLNP-2011-(05-09-2013)-FORM-2.pdf | 2013-09-05 |
| 28 | 617-KOLNP-2011-FER.pdf | 2016-10-19 |
| 29 | 617-KOLNP-2011-(05-09-2013)-FORM-3.pdf | 2013-09-05 |
| 29 | Other Patent Document [23-01-2017(online)].pdf | 2017-01-23 |
| 30 | 617-KOLNP-2011-(05-09-2013)-FORM-5.pdf | 2013-09-05 |
| 30 | Other Document [03-04-2017(online)].pdf | 2017-04-03 |
| 31 | 617-KOLNP-2011-(05-09-2013)-FORM-6.pdf | 2013-09-05 |
| 31 | Examination Report Reply Recieved [03-04-2017(online)].pdf | 2017-04-03 |
| 32 | 617-KOLNP-2011-(05-09-2013)-OTHERS.pdf | 2013-09-05 |
| 32 | Description(Complete) [03-04-2017(online)].pdf_137.pdf | 2017-04-03 |
| 33 | 617-KOLNP-2011-(05-09-2013)-PA.pdf | 2013-09-05 |
| 33 | Description(Complete) [03-04-2017(online)].pdf | 2017-04-03 |
| 34 | 617-kolnp-2011-abstract.pdf | 2011-10-06 |
| 34 | Correspondence [03-04-2017(online)].pdf | 2017-04-03 |
| 35 | Claims [03-04-2017(online)].pdf | 2017-04-03 |
| 35 | 617-kolnp-2011-claims.pdf | 2011-10-06 |
| 36 | 617-KOLNP-2011-CORRESPONDENCE 1.1.pdf | 2011-10-06 |
| 36 | Petition Under Rule 137 [04-04-2017(online)].pdf_465.pdf | 2017-04-04 |
| 37 | 617-kolnp-2011-correspondence.pdf | 2011-10-06 |
| 37 | Petition Under Rule 137 [04-04-2017(online)].pdf | 2017-04-04 |
| 38 | 617-kolnp-2011-description (complete).pdf | 2011-10-06 |
| 38 | 617-KOLNP-2011-FORM 13 [19-06-2019(online)].pdf | 2019-06-19 |
| 39 | 617-kolnp-2011-drawings.pdf | 2011-10-06 |
| 39 | 617-KOLNP-2011-Further evidence (MANDATORY) [25-07-2019(online)].pdf | 2019-07-25 |
| 40 | 617-KOLNP-2011-Annexure (Optional) [25-07-2019(online)].pdf | 2019-07-25 |
| 40 | 617-KOLNP-2011-FORM 18.pdf | 2011-10-06 |
| 41 | 617-kolnp-2011-form-1.pdf | 2011-10-06 |
| 41 | 617-KOLNP-2011-Written submissions and relevant documents (MANDATORY) [05-11-2019(online)].pdf | 2019-11-05 |
| 42 | 617-kolnp-2011-form-2.pdf | 2011-10-06 |
| 42 | 617-KOLNP-2011-PETITION UNDER RULE 137 [05-11-2019(online)].pdf | 2019-11-05 |
| 43 | 617-kolnp-2011-form-3.pdf | 2011-10-06 |
| 43 | 617-KOLNP-2011-PETITION UNDER RULE 137 [05-11-2019(online)]-1.pdf | 2019-11-05 |
| 44 | 617-kolnp-2011-form-5.pdf | 2011-10-06 |
| 44 | 617-KOLNP-2011-PatentCertificate06-11-2019.pdf | 2019-11-06 |
| 45 | 617-KOLNP-2011-IntimationOfGrant06-11-2019.pdf | 2019-11-06 |
| 45 | 617-kolnp-2011-international publication.pdf | 2011-10-06 |
| 46 | 617-KOLNP-2011-RELEVANT DOCUMENTS [20-02-2020(online)].pdf | 2020-02-20 |
| 46 | 617-kolnp-2011-international search report.pdf | 2011-10-06 |
| 47 | 617-kolnp-2011-others pct form.pdf | 2011-10-06 |
| 47 | 617-KOLNP-2011-FORM 4 [25-02-2020(online)].pdf | 2020-02-25 |
| 48 | 617-KOLNP-2011-RELEVANT DOCUMENTS [26-07-2021(online)].pdf | 2021-07-26 |
| 48 | 617-KOLNP-2011-PA.pdf | 2011-10-06 |
| 49 | 617-KOLNP-2011-RELEVANT DOCUMENTS [23-09-2022(online)].pdf | 2022-09-23 |
| 49 | 617-kolnp-2011-pct priority document notification.pdf | 2011-10-06 |
| 50 | 617-KOLNP-2011-RELEVANT DOCUMENTS [30-08-2023(online)].pdf | 2023-08-30 |
| 50 | 617-kolnp-2011-specification.pdf | 2011-10-06 |