CA2234130A1 - Alumina wood modification-decay, stain, and termite protection - Google Patents
Alumina wood modification-decay, stain, and termite protection Download PDFInfo
- Publication number
- CA2234130A1 CA2234130A1 CA 2234130 CA2234130A CA2234130A1 CA 2234130 A1 CA2234130 A1 CA 2234130A1 CA 2234130 CA2234130 CA 2234130 CA 2234130 A CA2234130 A CA 2234130A CA 2234130 A1 CA2234130 A1 CA 2234130A1
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- wood
- decay
- aluminate
- salts
- aluminates
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Abstract
A method for chemically modifying wood with reactive alumina which consists of contacting said wood with aluminates chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts; and a method for the wood decay and staining protection which results. A method for expanding the wood protection to prevent termites by adding ethanolamine copper complexes.
Description
Alumina Wood ~odification-Decay, Stain, and Termite Protection The present invention relates to a method for chemically modifying wood with reactive ionic alumina derived from sodium aluminate or p~tassium aluminate, the decay and stain resistance which results, and t]he termite resistance noted when copper complexes are added to the wood modifying agents.
Background of the Invention Wood is commonly protected from decay and stains by treating with toxic chemicals which are water insoluble or become water insoluble in the wood. These toxic chemicals represent hazards to humans and the environment. Protecting wood by chemical modification of the wood cellulose with substances common in the environment represents an ideal solution to the problems posed by fungicidal wood treating chemicals. Copper is one of the more permanent, and least hazardous wood termite inhibitors.
Cellulose modification is discussed with clarity by Dr.
R. G. Siu in Microbial Decomposition of Cellulose. Dr. Siu discusses the advantages of protecting cellulose from decay by modification rather than using toxic substances for protection. The requirements he outlines for an ideal modification method are mostly met by sodium and potassium aluminates. Wood modification according to the teaching of Dr.
Siu has not become a commercial reality. It is believed the modification treatments attempted did not fix well.
It is one object of my invention to protect wood from decay and from many undesirable wood stains without the use of anionic fungicidal chemicals. These anionic chemicals may react with the aluminates and render them unsuitable for cellulose modification. The aluminum salts formed may protect the wood;
but that protection is from the anionic portion of the salt.
It is possible to use the aluminates in stoichiometric excess of the added anions, and thus achieve wood modification in the presence of anionic fungicides. This approach leads to r~dundant protection from decay and stains. It is also possible to use fun~icidal anions at less than fungicidal levels with the aluminates of my invention in an effort to circumvent my claims. My invention precludes fungicidally effective amounts of certain anions with the aluminates.
The sodium aluminate and potassium aluminate used in the practice of my invention have a long history of use in paper making, in water purification, and in other commercial processes.
In none of these applications do the aluminates exhibit fungicidal activity. The alumina from the aluminates which modify the cellulose occurs commonly in the environment, and certainly is no fungicide. In fact aluminum is the third most common element found in the environment.
It is known that certain aluminum or alumina salts, like salts of calcium and potassium, have fungicidal activity.
Aluminum salts of N-nitrosocyclohexylhydroxylamine compounds and aluminum salts of certain phosphonic acids are known to be fungicides. My invention does not encompass treating wood with aluminum salts whether or not those salts inhibit fungi.
Those skilled in the art will recognize that references in the literature to compositions prepared by adding sodium aluminate or potassium aluminate with acids or salts does not mean these Eormulations contain sodium aluminate or potassium aluminate once they are mixed together. The aluminates are low cost sources of water soluble aluminum often used for the preparation of aluminum salts. They offer the formulation chemist an opportunity to prepare creative compositions containing aluminum compounds.
When acids or acidic salts are mixed with aluminates, the salts of aluminum and acid anions are formed. When alkaline salts and aluminates are mixed together, the aluminum salts of the alkal:ine salt anions are formed providing those aluminum salts are less water soluble or less ionized than the alkaline salts. When phosphonic acids are mixed with aluminates, aluminum phosphonate salts are formed. When water soluble salts of N-nitrosocyclohexylhydroxylamine are mixed with aluminates, the aluminum salts of this fungicidal anion are formed. These salts, like most other insoluble aluminum salts, are soluble in solutions containing alkali hydroxides.
While additives, which convert reactive alumina to aluminum salts, can not be used in the practice of my invention, other additives may be used if they do not change the ionic nature of the alumina. Treated wood leaching tests can indicate whether anionic additives form aluminum salts when used with aluminates.
If the anion leaches little, it has formed an insoluble aluminum salt. If it: leaches much, there is no legitimate reason for its presence in a system which requires permanence.
Wood is treated in the practice of my invention by contacting it with concentrations of sodium aluminate, potassium aluminate, or a combination of these. The treating concentrations may also contain acceptable additives. The wood may be contacted by any suitable means such as brushing, spraying, dipping, soaking, pressure treating, or by applying a bandage. Contacting methods which result in greater aluminate concentration retentions require less aluminate in the treating concentration for effective wood modification. I have found at least a 0.5%
aluminate concentration is required for consistently effective protection from decay and staining even when treating methods are used which result in the highest retentions. The treating concentration best for a specific treating application can only be determined by extensive testing of treated wood. A suitable concentration for one species of wood may not be suitable for another species.
Additives especially useful in the alumina wood modification treatments are those capable of protecting the wood from insect attack. I have found that certain cationic copper complexes produced by reacting copper or copper compounds with ammonia or amines are useful additives which provide insect protection to treated wood, and do not negate the decay protection afforded by alumina wood modification. The copper is cationic and can not react with cationic alumina. Several cationic copper complexes are available commercially.
Summary of the Invention The present invention comprises a method for chemically modifying wood with reactive alumina, which consists of contacting said wood with aluminates chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts.-The current invention additionally comprises a method for protecting wood from decay and staining, which consists of contacting said wood with reactive alumina derived from aluminates, chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts. My invention further comprises a method for protecting wood from decay and termites, which consists of contacting said wood with reactive alumina, derived from aluminates, chosen from the group consisting of sodium aluminate and potassium aluminate, in concentrations greater than 0.5%, with ethanolamine copper complexes added, but without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts.
Detailed Description of the Invention The following examples illustrate contacting wood with aluminate concentrations so as to achieve alumina wood modification, contacting wood with aluminate concentrations plus ethanolamine copper complexes so as to achieve alumina wood modification and copper insecticidal protection, and the performance of the treated wood when it was exposed in Tate County, Mississippi, U.S.A.
Example 1 A fresh cut and peeled pine pole was wrapped on one end with a towel which had been spread with a one-fourth inch thickness of 95% sodium aluminate powder. After one week, the towel was removed and the pole exposed in the weather for six weeks. After this exposure, the pole was free of stain in the treated area, but badly discolored where it was not contacted by the aluminate. After another year of exposure above ground, the untreated end of the pole was infected with decay while the treated end was bright and free of decay.
Example 2 Seasoned pine boards, free of stain, were full cell treated with a 0.5% concentration of sodium aluminate in water. These, and untreated boards, were placed outdoors on the ground for six weeks. At the end of this period only the treated boards were free of stain.
Example 3 Seasonecl pine boards were full cell treated with a 5%
concentration of sodium aluminate in water. These, and untreated boards, were placed in a forest area, and covered with two inches of soil. After a period of two years the untreated boards were destroyed by decay and insects. After the same period, the treated boards were attacked by insects; but they were not attacked by decay.
Example 4 A fresh cut and peeled elm pole, which contained a heavy concentration of sugars near the surface, was treated on one end, with a 10% concentration of sodium aluminate in water, by brush coat. This treating was performed during the middle of the summer when mold growth is most prolific. This pole was-exposed where mold spores were regularly stirred by grass mowing.
At the end of two weeks mold growth was prolific on both ends.
The pole was allowed to remain exposed above ground for another year. At the end of the year, the untreated end was decayed on the surface while the treated end was free of decay. The aluminate treatment modified the cellulose and it was not used by decay organisms. The aluminate did not modify the wood sugars, and they were available to support mold growth.
Example 5 Western red cedar siding was removed from a house where it had darkened over a period of years. One end of each board was brush coated with a 10% solution of sodium aluminate in water. The center portion was left untreated while the opposite end was brush coated with a 10% solution of sodium hydroxide in water. After one week of outdoor exposure, the treated ends were both bleached, with the sodium aluminate treatment being somewhat whiter than the sodium hydroxide treatment. After another year of outdoor exposure, the sodium hydroxide treatment had stained while the sodium aluminate treatment rem~;ned bright and free of stain. The untreated center of the boards did not change significantly during this period.
Example 6 A fresh cut and peeled hackberry pole, which contained a heavy concentration of sugars near the surface, was treated on one end with a 10% concentration of potassium aluminate in water. The treating and early testing was performed as in Example 4. After two weeks, molds covered the untreated and treated ends. After another two months of exposure, the treated end was again brush coated with 10% potassium aluminate in water.
This bleached out the mold growth after one week of exposure~
After another year of exposure, the treated end remained free of both molds and decay, while the untreated end was molded and decayed.
Example 7 One end of pine boards were soaked for one week in water solutions containing 2% sodium aluminate and 2% potassium aluminate. The opposite end of the boards remained untreated.
The boards were exposed in a forest area where they were covered with two inches of soil. At the end of a three year period, the untreated ends of the boards were destroyed by decay and termites. At the end of the three year period the treated ends of the boards were free of decay. They were-attacked by termites;
but the degree of attack was much less than the termite attack on the untreated ends.
Example 8 One end of pine boards were soaked for one week in a water solution containing 3% sodium aluminate. The center of the boards was left untreated. The opposite ends of these boards were later soaked for one week in a water solution containing 3% sodium aluminate plus 0.1~ copper derived from a commercial ethanolamine copper complex product. These boards were dried, then exposed in a forest area under two inches of soil. At the end of a three year period, the centers of the boards were destroyed by decay and termites. The ends treated with 3% sodium aluminate were free of decay, but exhibited some termite attack. The ends treated with 3% sodium aluminate plus 0.1% copper were free of attack by both decay and termites.
Background of the Invention Wood is commonly protected from decay and stains by treating with toxic chemicals which are water insoluble or become water insoluble in the wood. These toxic chemicals represent hazards to humans and the environment. Protecting wood by chemical modification of the wood cellulose with substances common in the environment represents an ideal solution to the problems posed by fungicidal wood treating chemicals. Copper is one of the more permanent, and least hazardous wood termite inhibitors.
Cellulose modification is discussed with clarity by Dr.
R. G. Siu in Microbial Decomposition of Cellulose. Dr. Siu discusses the advantages of protecting cellulose from decay by modification rather than using toxic substances for protection. The requirements he outlines for an ideal modification method are mostly met by sodium and potassium aluminates. Wood modification according to the teaching of Dr.
Siu has not become a commercial reality. It is believed the modification treatments attempted did not fix well.
It is one object of my invention to protect wood from decay and from many undesirable wood stains without the use of anionic fungicidal chemicals. These anionic chemicals may react with the aluminates and render them unsuitable for cellulose modification. The aluminum salts formed may protect the wood;
but that protection is from the anionic portion of the salt.
It is possible to use the aluminates in stoichiometric excess of the added anions, and thus achieve wood modification in the presence of anionic fungicides. This approach leads to r~dundant protection from decay and stains. It is also possible to use fun~icidal anions at less than fungicidal levels with the aluminates of my invention in an effort to circumvent my claims. My invention precludes fungicidally effective amounts of certain anions with the aluminates.
The sodium aluminate and potassium aluminate used in the practice of my invention have a long history of use in paper making, in water purification, and in other commercial processes.
In none of these applications do the aluminates exhibit fungicidal activity. The alumina from the aluminates which modify the cellulose occurs commonly in the environment, and certainly is no fungicide. In fact aluminum is the third most common element found in the environment.
It is known that certain aluminum or alumina salts, like salts of calcium and potassium, have fungicidal activity.
Aluminum salts of N-nitrosocyclohexylhydroxylamine compounds and aluminum salts of certain phosphonic acids are known to be fungicides. My invention does not encompass treating wood with aluminum salts whether or not those salts inhibit fungi.
Those skilled in the art will recognize that references in the literature to compositions prepared by adding sodium aluminate or potassium aluminate with acids or salts does not mean these Eormulations contain sodium aluminate or potassium aluminate once they are mixed together. The aluminates are low cost sources of water soluble aluminum often used for the preparation of aluminum salts. They offer the formulation chemist an opportunity to prepare creative compositions containing aluminum compounds.
When acids or acidic salts are mixed with aluminates, the salts of aluminum and acid anions are formed. When alkaline salts and aluminates are mixed together, the aluminum salts of the alkal:ine salt anions are formed providing those aluminum salts are less water soluble or less ionized than the alkaline salts. When phosphonic acids are mixed with aluminates, aluminum phosphonate salts are formed. When water soluble salts of N-nitrosocyclohexylhydroxylamine are mixed with aluminates, the aluminum salts of this fungicidal anion are formed. These salts, like most other insoluble aluminum salts, are soluble in solutions containing alkali hydroxides.
While additives, which convert reactive alumina to aluminum salts, can not be used in the practice of my invention, other additives may be used if they do not change the ionic nature of the alumina. Treated wood leaching tests can indicate whether anionic additives form aluminum salts when used with aluminates.
If the anion leaches little, it has formed an insoluble aluminum salt. If it: leaches much, there is no legitimate reason for its presence in a system which requires permanence.
Wood is treated in the practice of my invention by contacting it with concentrations of sodium aluminate, potassium aluminate, or a combination of these. The treating concentrations may also contain acceptable additives. The wood may be contacted by any suitable means such as brushing, spraying, dipping, soaking, pressure treating, or by applying a bandage. Contacting methods which result in greater aluminate concentration retentions require less aluminate in the treating concentration for effective wood modification. I have found at least a 0.5%
aluminate concentration is required for consistently effective protection from decay and staining even when treating methods are used which result in the highest retentions. The treating concentration best for a specific treating application can only be determined by extensive testing of treated wood. A suitable concentration for one species of wood may not be suitable for another species.
Additives especially useful in the alumina wood modification treatments are those capable of protecting the wood from insect attack. I have found that certain cationic copper complexes produced by reacting copper or copper compounds with ammonia or amines are useful additives which provide insect protection to treated wood, and do not negate the decay protection afforded by alumina wood modification. The copper is cationic and can not react with cationic alumina. Several cationic copper complexes are available commercially.
Summary of the Invention The present invention comprises a method for chemically modifying wood with reactive alumina, which consists of contacting said wood with aluminates chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts.-The current invention additionally comprises a method for protecting wood from decay and staining, which consists of contacting said wood with reactive alumina derived from aluminates, chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts. My invention further comprises a method for protecting wood from decay and termites, which consists of contacting said wood with reactive alumina, derived from aluminates, chosen from the group consisting of sodium aluminate and potassium aluminate, in concentrations greater than 0.5%, with ethanolamine copper complexes added, but without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts.
Detailed Description of the Invention The following examples illustrate contacting wood with aluminate concentrations so as to achieve alumina wood modification, contacting wood with aluminate concentrations plus ethanolamine copper complexes so as to achieve alumina wood modification and copper insecticidal protection, and the performance of the treated wood when it was exposed in Tate County, Mississippi, U.S.A.
Example 1 A fresh cut and peeled pine pole was wrapped on one end with a towel which had been spread with a one-fourth inch thickness of 95% sodium aluminate powder. After one week, the towel was removed and the pole exposed in the weather for six weeks. After this exposure, the pole was free of stain in the treated area, but badly discolored where it was not contacted by the aluminate. After another year of exposure above ground, the untreated end of the pole was infected with decay while the treated end was bright and free of decay.
Example 2 Seasoned pine boards, free of stain, were full cell treated with a 0.5% concentration of sodium aluminate in water. These, and untreated boards, were placed outdoors on the ground for six weeks. At the end of this period only the treated boards were free of stain.
Example 3 Seasonecl pine boards were full cell treated with a 5%
concentration of sodium aluminate in water. These, and untreated boards, were placed in a forest area, and covered with two inches of soil. After a period of two years the untreated boards were destroyed by decay and insects. After the same period, the treated boards were attacked by insects; but they were not attacked by decay.
Example 4 A fresh cut and peeled elm pole, which contained a heavy concentration of sugars near the surface, was treated on one end, with a 10% concentration of sodium aluminate in water, by brush coat. This treating was performed during the middle of the summer when mold growth is most prolific. This pole was-exposed where mold spores were regularly stirred by grass mowing.
At the end of two weeks mold growth was prolific on both ends.
The pole was allowed to remain exposed above ground for another year. At the end of the year, the untreated end was decayed on the surface while the treated end was free of decay. The aluminate treatment modified the cellulose and it was not used by decay organisms. The aluminate did not modify the wood sugars, and they were available to support mold growth.
Example 5 Western red cedar siding was removed from a house where it had darkened over a period of years. One end of each board was brush coated with a 10% solution of sodium aluminate in water. The center portion was left untreated while the opposite end was brush coated with a 10% solution of sodium hydroxide in water. After one week of outdoor exposure, the treated ends were both bleached, with the sodium aluminate treatment being somewhat whiter than the sodium hydroxide treatment. After another year of outdoor exposure, the sodium hydroxide treatment had stained while the sodium aluminate treatment rem~;ned bright and free of stain. The untreated center of the boards did not change significantly during this period.
Example 6 A fresh cut and peeled hackberry pole, which contained a heavy concentration of sugars near the surface, was treated on one end with a 10% concentration of potassium aluminate in water. The treating and early testing was performed as in Example 4. After two weeks, molds covered the untreated and treated ends. After another two months of exposure, the treated end was again brush coated with 10% potassium aluminate in water.
This bleached out the mold growth after one week of exposure~
After another year of exposure, the treated end remained free of both molds and decay, while the untreated end was molded and decayed.
Example 7 One end of pine boards were soaked for one week in water solutions containing 2% sodium aluminate and 2% potassium aluminate. The opposite end of the boards remained untreated.
The boards were exposed in a forest area where they were covered with two inches of soil. At the end of a three year period, the untreated ends of the boards were destroyed by decay and termites. At the end of the three year period the treated ends of the boards were free of decay. They were-attacked by termites;
but the degree of attack was much less than the termite attack on the untreated ends.
Example 8 One end of pine boards were soaked for one week in a water solution containing 3% sodium aluminate. The center of the boards was left untreated. The opposite ends of these boards were later soaked for one week in a water solution containing 3% sodium aluminate plus 0.1~ copper derived from a commercial ethanolamine copper complex product. These boards were dried, then exposed in a forest area under two inches of soil. At the end of a three year period, the centers of the boards were destroyed by decay and termites. The ends treated with 3% sodium aluminate were free of decay, but exhibited some termite attack. The ends treated with 3% sodium aluminate plus 0.1% copper were free of attack by both decay and termites.
Claims (3)
1. A method for chemically modifying wood with reactive alumina which consists of contacting said wood with aluminates chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts.
2. A method for protecting wood from decay and staining, which consists of contacting said wood with reactive alumina derived from aluminates, chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts.
3. A method for protecting wood from decay and termites, which consists of contacting said wood with reactive alumina derived from aluminates, chosen from the group consisting of sodium aluminate and potassium aluminate in concentrations greater than 0.5%, with ethanolamine copper complexes added; but without fungicidally effective amounts of anions from N-nitrosocyclohexylhydroxylamine salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87836497A | 1997-06-18 | 1997-06-18 | |
| US08/878,364 | 1997-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2234130A1 true CA2234130A1 (en) | 1998-12-18 |
Family
ID=25371890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2234130 Abandoned CA2234130A1 (en) | 1997-06-18 | 1998-04-01 | Alumina wood modification-decay, stain, and termite protection |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2234130A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019004846A1 (en) * | 2017-06-27 | 2019-01-03 | Wood Modification Technologies Limited | Enhanced performance of wood and engineered wood products using combined durability and flame retardancy |
-
1998
- 1998-04-01 CA CA 2234130 patent/CA2234130A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019004846A1 (en) * | 2017-06-27 | 2019-01-03 | Wood Modification Technologies Limited | Enhanced performance of wood and engineered wood products using combined durability and flame retardancy |
| US11370146B2 (en) | 2017-06-27 | 2022-06-28 | Wood Modification Technologies Limited | Enhanced performance of wood and engineered wood products using combined durability and flame retardancy |
| US11628590B2 (en) | 2017-06-27 | 2023-04-18 | Wood Modification Technologies Limited | Enhanced performance of wood and engineered wood products using combined durability and flame retardancy |
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