CA1157055A - Refractory - Google Patents
RefractoryInfo
- Publication number
- CA1157055A CA1157055A CA000375615A CA375615A CA1157055A CA 1157055 A CA1157055 A CA 1157055A CA 000375615 A CA000375615 A CA 000375615A CA 375615 A CA375615 A CA 375615A CA 1157055 A CA1157055 A CA 1157055A
- Authority
- CA
- Canada
- Prior art keywords
- refractory
- weight
- nitride
- aluminum
- batch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
Abstract
REFRACTORY
Abstract of the Disclosure A means for producing nitride bonded refractory shapes, in situ, by mixing an aluminum metal powder, relatively pure silica and a refractory aggregate. The mixes are pressed into shapes and burned at elevated temperatures in a nitriding atmosphere to form the bond.
Abstract of the Disclosure A means for producing nitride bonded refractory shapes, in situ, by mixing an aluminum metal powder, relatively pure silica and a refractory aggregate. The mixes are pressed into shapes and burned at elevated temperatures in a nitriding atmosphere to form the bond.
Description
7V~
REFRACTORY
Silicon nitride, aluminum nitride and aluminum oxide in the form of fine powders when thoroughly and uniformly mixed in suitable proportions, and heated at elevated temperatures, can provide ceramics which have relatively good high temperature properties and application in excess of 1400C. Nitride compounds referred to as sialon compounds have been synthesized by mixing alpha and/or beta silicon nitride with alpha and/or gamma alumina powder. Sialon generally means an intimate dispersion of alumina oxide throughout a silicon nitride matrix. It is believed that upon sinteringJ the material becomes a solid solution of aluminum oxide in silicon nitride. The letters which make up the term "sialon" are the letters taken from the chemical abbreviation for the elements therein, that is, silicon, aluminum, oxygen and nitrogen.
Considerable effort has been directed to the development of ceramic articles containing 80~ and more of silicon nitride, silicon oxynitride and/or sialon. These articles consist predominantly of single phase nitrides and display good thermal shock resistance, strength and corrosion resistance. Little information exists in the utilization of these nitride phases as the bonding agent in conventional refractories. Several limiting factors which have retarded large scale development of nitride bonded refractories include the high cost of purchased silicon ,, . .- . .
. . : ~. ,,: . ,, : ~ .
7~55 nitride, the instability of certain oxynitrides at high temperature, and the hydrolizing tendency of possible starting materials, such as, aluminum nitride and magnesium nitride. To overcome these obstacles, it would be advantageous to form, in situ, nitride phases by the addition of a single metallic metal powder which can react with gaseous nitrogen to produce a crystalline nitride phase capable of ceramic bonding to relatively inexpensive refractory grains. This approach will greatly lower the cost of nitride articles and couple the distinct advantages of nitride compounds to the established advantages of conventional refractory grains.
It is an object of the present invention to produce nitride bonded refractories with improved physical properties compared to refractories made with the addition - of two or more reactive metal powders.
Another object of the invention is to join a sialon and other nitride phases with conventional refractory grains which are typically bonded by oxides which can be readily decomposed by certain metals to provide properties, such as, non-wetability by molten metals, resistance to chlorine attack and low thermal expansion.
A further object of the invention is to provide nitride bonded refractories having improved porosity and ~5 relatively good room temperature and elevated temperature strength.
In accordance with the present invention, there is provided a method for producing nitride bonded refràctory shapes in situ. A mixture is prepared comprising about 1 to 25%, by weight, aluminum, about 1 to 25%, by weight, substantially pure silica and the balance a refractory brick making size graded refractory aggregate.
The mixes are pressed into refractory shapes and burned at elevated temperatures in a nitriding atmosphere to form the nitride bond.
In a preferred embodiment, the aluminum comprises about 1 to 16% and the substantially pure silica comprises about 1.5 to 20~, by weight, of the mix. The shapes are preferably burned at a temperature between about 1090 and :
5~
1750C and the nitriding~atmosphere is composed o~ either gaseous nitrogen, industrial annealing gas, or ammonia gas.
I'he refractory aggregate is preferably selected from silicon carbide, fused mullite and magnesite.
In a nitrogen atmosphere, at elevated temperatures, aluminum reduces silica forming silicon, alumina, aluminum nitride and gamma aluminum oxynitride.
With additional treatment at elevated temperatures, silicon is nitrided to form beta silicon nitride and the alumina, aluminum nitride and aluminum oxynitride enters into the silicon nitride structure as a solid solution to form beta prime sialon. During firing it is always possible that minor levels of oxygen may enter into the chamber confining the refractories. In such an event, the formation of a pure beta prime sialon is hampered and the so-called "X", "J" or aluminum nitride polytypes may also form.
During nitriding, the metallic phase undergoes a gas-metal reaction and forms minute crystals surrounding the metal nucleus. Maintaining a hold during the firing process ensures drainage of the metal from the nucleus through the pores of the crystalline mat which allows additional nitridization of the metal. During the end of the hold period, true ceramic bonding is achieved with the coarse refractory grains by virtue of their solubility in the nitride phases.
To successfully achieve nitridization and also an economical firing schedule, it is preferred that the starting metal powder be as fine as possible. Generally, the aluminum powder should have an average particle diameter of about 34 microns with 90% of the particles being finer than 70 microns. The silica used in the mixes may have one or more ranges of particle size. For instance, extremely fine silica can be used which has an average particle diameter of less than about 1 micron. However, incorporation of large quantities of this exceedingly fine material to a refractory mix, often results in pressing difficulties. It is advantageous to add the very fine silica with a coarser form of silica to obtain the large amount of silica needed in the mix.
:~57'i~5 It is also preferred that the reactive material not exceed about 20~ of the mix for economic reasons. Also, larger quantities do not result in articles with materially improved physical properties.
In the following examples, illustrated below, aluminum powder was mixed with silica and either silicon carbide, fused mullite or magnesite. A solution of dextrin and/or lignin liquor and water was used as a temporary binder. The mixes were formed into shapes by power pressing to about 18,000 psi. The brick were then fired in the presence of flowing nitrogen to a temperature of about 2600F with a holding time of about four hours. Mixes were also prepared containing a combination of both aluminum and silicon metal powders. The overall results indicated that the mixes made with only a single metal addition was stronger and less porous than mixes made with the two metal additions. The various bonding phases are also shown in Table I.
, 7~5 .5 .
a~
o\ o~ oP oP CO U~ ~
~o o In U~ o . o :>, I I t~~1 1 ~ ~ ~D I ~
~1 ~1 0 g o~o oP oP o~O U~ o , o ~o ~. ~
a~ ~1 ~ ~1 1 ~1 I I I ,1 ~ U~
.~ .
q) .
o~o o~O oP CO o ~r ~ ~ . u~ t~
, I ~I I ,, ~
a~ o oPoP oP oP oP ~ o ~ N I m ~ u~
H
. a) ~
o\ OP ~o o\O a~ o . ~ u~
~ ~ I ~
m E~ d~O ~ O O
~ ~ o~o ~o Op . C~ ~1 ~ rl m ~ u~
d~ o\ d~ d~ a~ o o U~ O O U~ . O
m ~ u~
d~ oP o\ ~
O ~
m ~ ta .q ~ o ~ ~
R ~ ~ u tn ~ ~Qo o ~ o O
o ~ ~ ~ o ~ ~ m o ~ o ~ ~ o U ~ I~ ~ U ~ ~rl U U
~_~ -~ l ~ ~o o h ~ u~ ~ a u~
O L~ O
. ., .. I
! ' . ' ' : : ' .
. ~, :. . .. -In the above mixes, the refractory aggregate was sized such that about 5 to 22% was retained on a 10 mesh screen, about 23 to 36% was -10+28 mesh, about 8 to 25% was -28+65 mesh, about 7 to 10% was -65+200 mesh and about 30 to 35% passed a 200 mesh screen. All of the above mesh sizes are based upon the Tyler standard series.
As to the raw materials used above, the aluminum powder was pure aluminum metal, and the silica analyzed in excess of 98% SiO2. The refractory aggregate used in the examples have the approximate chemical analysis as shown in Table II below.
TABLE II
Silicon Fused Deadburned Carbide Mullite Magensite SiO2 - 22.9% 0.7 A123 0 4 76.4 0.2 TiO2 0.1 0.1 -Fe2O3 0.8 0.3 0.2 CaO 0.2 - 0.6 MgO 0.02 - 98.3 Alk. 0.03 0.35 Calculated SiC 96.5 - -All of the chemical analyses are based on an oxide analysis which would not indicate the carbon content of the silicon carbide.
. ~
.' :
REFRACTORY
Silicon nitride, aluminum nitride and aluminum oxide in the form of fine powders when thoroughly and uniformly mixed in suitable proportions, and heated at elevated temperatures, can provide ceramics which have relatively good high temperature properties and application in excess of 1400C. Nitride compounds referred to as sialon compounds have been synthesized by mixing alpha and/or beta silicon nitride with alpha and/or gamma alumina powder. Sialon generally means an intimate dispersion of alumina oxide throughout a silicon nitride matrix. It is believed that upon sinteringJ the material becomes a solid solution of aluminum oxide in silicon nitride. The letters which make up the term "sialon" are the letters taken from the chemical abbreviation for the elements therein, that is, silicon, aluminum, oxygen and nitrogen.
Considerable effort has been directed to the development of ceramic articles containing 80~ and more of silicon nitride, silicon oxynitride and/or sialon. These articles consist predominantly of single phase nitrides and display good thermal shock resistance, strength and corrosion resistance. Little information exists in the utilization of these nitride phases as the bonding agent in conventional refractories. Several limiting factors which have retarded large scale development of nitride bonded refractories include the high cost of purchased silicon ,, . .- . .
. . : ~. ,,: . ,, : ~ .
7~55 nitride, the instability of certain oxynitrides at high temperature, and the hydrolizing tendency of possible starting materials, such as, aluminum nitride and magnesium nitride. To overcome these obstacles, it would be advantageous to form, in situ, nitride phases by the addition of a single metallic metal powder which can react with gaseous nitrogen to produce a crystalline nitride phase capable of ceramic bonding to relatively inexpensive refractory grains. This approach will greatly lower the cost of nitride articles and couple the distinct advantages of nitride compounds to the established advantages of conventional refractory grains.
It is an object of the present invention to produce nitride bonded refractories with improved physical properties compared to refractories made with the addition - of two or more reactive metal powders.
Another object of the invention is to join a sialon and other nitride phases with conventional refractory grains which are typically bonded by oxides which can be readily decomposed by certain metals to provide properties, such as, non-wetability by molten metals, resistance to chlorine attack and low thermal expansion.
A further object of the invention is to provide nitride bonded refractories having improved porosity and ~5 relatively good room temperature and elevated temperature strength.
In accordance with the present invention, there is provided a method for producing nitride bonded refràctory shapes in situ. A mixture is prepared comprising about 1 to 25%, by weight, aluminum, about 1 to 25%, by weight, substantially pure silica and the balance a refractory brick making size graded refractory aggregate.
The mixes are pressed into refractory shapes and burned at elevated temperatures in a nitriding atmosphere to form the nitride bond.
In a preferred embodiment, the aluminum comprises about 1 to 16% and the substantially pure silica comprises about 1.5 to 20~, by weight, of the mix. The shapes are preferably burned at a temperature between about 1090 and :
5~
1750C and the nitriding~atmosphere is composed o~ either gaseous nitrogen, industrial annealing gas, or ammonia gas.
I'he refractory aggregate is preferably selected from silicon carbide, fused mullite and magnesite.
In a nitrogen atmosphere, at elevated temperatures, aluminum reduces silica forming silicon, alumina, aluminum nitride and gamma aluminum oxynitride.
With additional treatment at elevated temperatures, silicon is nitrided to form beta silicon nitride and the alumina, aluminum nitride and aluminum oxynitride enters into the silicon nitride structure as a solid solution to form beta prime sialon. During firing it is always possible that minor levels of oxygen may enter into the chamber confining the refractories. In such an event, the formation of a pure beta prime sialon is hampered and the so-called "X", "J" or aluminum nitride polytypes may also form.
During nitriding, the metallic phase undergoes a gas-metal reaction and forms minute crystals surrounding the metal nucleus. Maintaining a hold during the firing process ensures drainage of the metal from the nucleus through the pores of the crystalline mat which allows additional nitridization of the metal. During the end of the hold period, true ceramic bonding is achieved with the coarse refractory grains by virtue of their solubility in the nitride phases.
To successfully achieve nitridization and also an economical firing schedule, it is preferred that the starting metal powder be as fine as possible. Generally, the aluminum powder should have an average particle diameter of about 34 microns with 90% of the particles being finer than 70 microns. The silica used in the mixes may have one or more ranges of particle size. For instance, extremely fine silica can be used which has an average particle diameter of less than about 1 micron. However, incorporation of large quantities of this exceedingly fine material to a refractory mix, often results in pressing difficulties. It is advantageous to add the very fine silica with a coarser form of silica to obtain the large amount of silica needed in the mix.
:~57'i~5 It is also preferred that the reactive material not exceed about 20~ of the mix for economic reasons. Also, larger quantities do not result in articles with materially improved physical properties.
In the following examples, illustrated below, aluminum powder was mixed with silica and either silicon carbide, fused mullite or magnesite. A solution of dextrin and/or lignin liquor and water was used as a temporary binder. The mixes were formed into shapes by power pressing to about 18,000 psi. The brick were then fired in the presence of flowing nitrogen to a temperature of about 2600F with a holding time of about four hours. Mixes were also prepared containing a combination of both aluminum and silicon metal powders. The overall results indicated that the mixes made with only a single metal addition was stronger and less porous than mixes made with the two metal additions. The various bonding phases are also shown in Table I.
, 7~5 .5 .
a~
o\ o~ oP oP CO U~ ~
~o o In U~ o . o :>, I I t~~1 1 ~ ~ ~D I ~
~1 ~1 0 g o~o oP oP o~O U~ o , o ~o ~. ~
a~ ~1 ~ ~1 1 ~1 I I I ,1 ~ U~
.~ .
q) .
o~o o~O oP CO o ~r ~ ~ . u~ t~
, I ~I I ,, ~
a~ o oPoP oP oP oP ~ o ~ N I m ~ u~
H
. a) ~
o\ OP ~o o\O a~ o . ~ u~
~ ~ I ~
m E~ d~O ~ O O
~ ~ o~o ~o Op . C~ ~1 ~ rl m ~ u~
d~ o\ d~ d~ a~ o o U~ O O U~ . O
m ~ u~
d~ oP o\ ~
O ~
m ~ ta .q ~ o ~ ~
R ~ ~ u tn ~ ~Qo o ~ o O
o ~ ~ ~ o ~ ~ m o ~ o ~ ~ o U ~ I~ ~ U ~ ~rl U U
~_~ -~ l ~ ~o o h ~ u~ ~ a u~
O L~ O
. ., .. I
! ' . ' ' : : ' .
. ~, :. . .. -In the above mixes, the refractory aggregate was sized such that about 5 to 22% was retained on a 10 mesh screen, about 23 to 36% was -10+28 mesh, about 8 to 25% was -28+65 mesh, about 7 to 10% was -65+200 mesh and about 30 to 35% passed a 200 mesh screen. All of the above mesh sizes are based upon the Tyler standard series.
As to the raw materials used above, the aluminum powder was pure aluminum metal, and the silica analyzed in excess of 98% SiO2. The refractory aggregate used in the examples have the approximate chemical analysis as shown in Table II below.
TABLE II
Silicon Fused Deadburned Carbide Mullite Magensite SiO2 - 22.9% 0.7 A123 0 4 76.4 0.2 TiO2 0.1 0.1 -Fe2O3 0.8 0.3 0.2 CaO 0.2 - 0.6 MgO 0.02 - 98.3 Alk. 0.03 0.35 Calculated SiC 96.5 - -All of the chemical analyses are based on an oxide analysis which would not indicate the carbon content of the silicon carbide.
. ~
.' :
Claims (12)
1. A method for producing nitride bonded refractory shapes, in situ, comprising mixing, by weight, from about 1 to 25% aluminum, about 1 to 25% substantially pure silica and the balance a refractory brickmaking size graded refractory aggregate, pressing said mixes into refractory shapes, and burning the shapes at an elevated temperature in a nitriding atmosphere for a time sufficient to form the nitride bond.
2. Method of claim 1 in which the refractory aggregate is selected from the group consisting of silicon carbide, fused mullite and deadburned magnesite.
3. Method of claim 1 in which the aluminum comprises, by weight, about 1 to 16% and the substantially pure silica comprises, by weight, about 1.5 to 20% of the mix.
4. Method of claim 1 in which the shapes are burned at a temperature between about 1090 and 1750°C.
5. Method of claim 1 in which the nitriding atmosphere is selected from the group consisting of gaseous nitrogen, industrial annealing gas and ammonia gas.
6. A nitride bonded refractory shape made from a batch consisting essentially, by weight, of about 1 to 25%
aluminum, about 1 to 25% substantially pure silica and the balance a refractory aggregate.
aluminum, about 1 to 25% substantially pure silica and the balance a refractory aggregate.
7. Shape of claim 6, in which the refractory aggregate is selected from the group consisting of silicon carbide, fused mullite and magnesite.
8. Shape of claim 6 in which the aluminum comprises, by weight, about 1 to 16% and the substantially pure silica comprises, by weight, about 1.5 to 20% of the batch.
9. Shape of claim 6 in which the nitride bond is at least one bond selected from the group consisting of beta prime sialon, silicon oxynitride, beta silicon nitride, alpha silicon nitride and magnesium sialon.
10. A refractory batch for producing nitride bonded refractory shapes, consisting essentially, by weight, of between about 1 to 25% aluminum, between about 1 to 25%
substantially pure silica and the balance a refractory ag-gregate.
substantially pure silica and the balance a refractory ag-gregate.
11. Batch of claim 10 in which the refractory aggregate is selected from the group consisting of silicon carbide, fused mullite and magnesite.
12. Batch of claim 10 in which the aluminum comprises, by weight, between about 1 to 16% and the sub-stantially pure silica comprises, by weight, between about 1.5 to 20% of the batch.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14960980A | 1980-05-14 | 1980-05-14 | |
US149,609 | 1988-01-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1157055A true CA1157055A (en) | 1983-11-15 |
Family
ID=22531073
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000375615A Expired CA1157055A (en) | 1980-05-14 | 1981-04-16 | Refractory |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS573765A (en) |
BR (1) | BR8102971A (en) |
CA (1) | CA1157055A (en) |
DE (1) | DE3119067A1 (en) |
IT (1) | IT1170941B (en) |
ZA (1) | ZA812568B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010071196A1 (en) * | 2008-12-18 | 2010-06-24 | 黒崎播磨株式会社 | Process for producing plate brick, and plate brick |
DE102020206957A1 (en) | 2020-06-03 | 2021-12-09 | Refratechnik Holding Gmbh | Dry backfill and backfill fresh mass for the production of a coarse ceramic, fired refractory product, in particular a pipe protection plate, made of nitride-bonded silicon carbide, such a product and method for its production and waste incineration plant, flue gas desulphurization system and melting tank with such a product |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1054631A (en) * | 1963-01-31 | 1967-01-11 | ||
GB1055231A (en) * | 1964-01-20 | 1967-01-18 | Morganite Res & Dev Ltd | Improvements in or relating to the production of refractory nitride articles |
GB1504141A (en) * | 1974-01-31 | 1978-03-15 | Advanced Materials Eng | Synthetic ceramic materials and methods of making them |
-
1981
- 1981-04-16 ZA ZA00812568A patent/ZA812568B/en unknown
- 1981-04-16 CA CA000375615A patent/CA1157055A/en not_active Expired
- 1981-05-04 IT IT48388/81A patent/IT1170941B/en active
- 1981-05-11 DE DE19813119067 patent/DE3119067A1/en not_active Withdrawn
- 1981-05-13 JP JP7211281A patent/JPS573765A/en active Pending
- 1981-05-13 BR BR8102971A patent/BR8102971A/en unknown
Also Published As
Publication number | Publication date |
---|---|
IT1170941B (en) | 1987-06-03 |
ZA812568B (en) | 1982-06-30 |
IT8148388A0 (en) | 1981-05-04 |
BR8102971A (en) | 1982-02-02 |
JPS573765A (en) | 1982-01-09 |
DE3119067A1 (en) | 1982-03-11 |
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