CN100462333C - Method of preparing SiC base multilayer tubular composite ceramic - Google Patents
Method of preparing SiC base multilayer tubular composite ceramic Download PDFInfo
- Publication number
- CN100462333C CN100462333C CNB2007100176314A CN200710017631A CN100462333C CN 100462333 C CN100462333 C CN 100462333C CN B2007100176314 A CNB2007100176314 A CN B2007100176314A CN 200710017631 A CN200710017631 A CN 200710017631A CN 100462333 C CN100462333 C CN 100462333C
- Authority
- CN
- China
- Prior art keywords
- paper
- ceramic
- minutes
- preparation
- sic
- 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 - Fee Related
Links
Images
Landscapes
- Ceramic Products (AREA)
Abstract
The invention discloses a making method of SiC based multiple-layered pipe-shaped composite ceramic, which comprises the following steps: adopting sol-gel technique to coat; proceeding carbon heat reduction reaction; sintering under normal pressure to prepare SiC based pipe-shaped composite ceramic; hydrolyzing certain proportion of anhydrous alcohol and ethyl silicate; adopting stronger ammonia water as catalyst; adjusting pH value to prepare the silicasol; soaking common paper in the prepared silicasol; drying; proceeding bionic design; making the multiple-layered pipe-shaped structure; immersing the structure into phenol resin to solidify and mould; carbonizing; sintering; draining silicon to obtain the product.
Description
Technical field
The present invention relates to a kind of preparation method of bionic ceramic, particularly a kind of preparation method of SiC/Si tubular composite ceramic.
Background technology
The moulding process of layered composite ceramic material mainly comprises at present: (1) prefabricated synusia stacks moulding: base layer and sandwich material are prefabricated film, stack successively in order to carry out press forming.(2) the dry powder layering is applied and put compression moulding: base layer and sandwich material are dry powder, apply to be placed in the mould successively to be pressed.(3) laminated into type behind the substrate coating sandwich material slurries: matrix is a prefabricated film, and sandwich material is a slip, stacks compression moulding after the coating.The applying method of sandwich material slip on base layer mainly contains: spraying method; Casting method; Dip coating.
In the preparation of SiC system layered composite ceramic, traditional method adopts above-mentioned composite molding technique mostly, and carries out hot pressed sintering.Wherein prefabricated substrate layer moulding process mainly adopts flow casting molding, rolling formation, injection forming, electrophoretic deposition etc., casting method with roll that embrane method is relative to be adopted more more extensively.But prefabricated substrate layer moulding process is comparatively complicated, adopts hot-pressing sintering technique to increase the manufacturing cost of product simultaneously.Therefore it is simple and easy to seek a kind of processing, the SiC basic unit shape composite ceramics forming preparation process that cost is low is that people thirst for always, as preparing the method for SiC basic unit shape composite ceramics as raw material by reaction in pressureless sintering, do not reach relevant patent but in existing disclosed document, see relevant report as yet with paper.
Summary of the invention
The present invention is directed to defectives such as the prefabricated substrate moulding of existing SiC basic unit shape composite ceramics and hot-pressing sintering technique preparation method complexity, cost of goods manifactured height is improved; a kind of method for preparing the SiC/Si tubular composite ceramic with paper as raw material by reaction in pressureless sintering is provided; this method can make full use of the designability of paper excellence; make complex-shaped large size ceramic member, can reduce cost of goods manifactured simultaneously again, save resource and protection environment.
In order to realize above-mentioned task, the present invention takes following technical scheme to be achieved:
1, silicon sol preparation: dehydrated alcohol, tetraethoxy and distilled water is in the ratio of 2:1:0.8, prehydrolysis 1 hour.Regulating the pH value with strong aqua is 9-11, under the stirring of induction stirring instrument, hydrolysis 2-6 hour, obtains silicon sol.
2, ceramic paper preparation: plain paper was soaked 40 minutes in the silicon sol for preparing, oven dry, ceramic paper is made in paper weightening finish 55%～65%.
3, tubulose specimen preparation: resol is diluted to 20%-40% concentration, the silica flour that is 10 μ m according to ratio and the median size of 1:2 is mixed with slurry, evenly is coated on the ceramic paper, makes the multilayer tubular sample by Bionic Design, 120 ℃ of oven dry in following 2-4 hour, curing molding.
4, charing: premolding multilayer tubular sample is placed in the carbon-tube oven, at N
2Under the gas shiled, be heated to 800 ℃ with the heat-up rate of 1 ℃/min, insulation 1h obtains paper carbon pipe;
5, sintering: the paper carbon pipe after the charing is put into plumbago crucible, then crucible is put into vacuum resistance furnace, vacuumize 40min after, stop to vacuumize after being heated to 800 ℃ with 5 ℃/min heat-up rate, feed N again
2Gas also continues to be heated to 1550 ℃ ± 10 ℃ with 2 ℃/min heat-up rate, insulation 20min～80min;
6, row's silicon: vacuumize once more after the insulation, and be warming up to 1650 ℃ ± 10 ℃, insulation 20min～40min promptly makes SiC/Si multilayer tubular composite ceramics after the cooling.
Method of the present invention is simple, and prepared ceramic material property satisfies service requirements.Zhi Bei SiC/Si multilayer tubular composite ceramics by this method, its flexural strength even have surpassed 200Mpa more than 100Mpa, have excellent mechanical property.In addition, preparation method of the present invention also has the following advantages: (1) pressureless sintering promptly need not sample is applied mechanical pressure in agglomerating siliconising, row's silicon process; (2) reaction in can be realized the dead size moulding, promptly no matter still can both keep the minimum change of specimen size behind final sintering in moulding; (3) raw material sources are extensive, cheap; (4) environment compatibility is good, can not pollute, and has " green ".
SiC/Si tubular composite ceramic with the inventive method preparation is mainly used in burn into wearing and tearing, hot environment, comprise industries such as metallurgy, petrochemical complex, machinery, electric power, mine, particularly complex-shaped large size ceramic members such as various pipes, pump, valve, housing have social value and economic worth widely.
Description of drawings
Fig. 1 the present invention is based on the process flow sheet that plain paper prepares the SiC/Si tubular composite ceramic.
Fig. 2 is the SEM photo of untreated plain paper;
Fig. 3 is the SEM photo of the ceramic paper handled through silicon sol;
Fig. 4 is the stereoscan photograph in the porous carbon sample transverse section after the charing;
Fig. 5 is the stereoscan photograph after the local amplification of the section of SiC/Si multilayer tubular composite ceramics;
Fig. 6 is a SiC/Si multilayer tubular composite ceramics pictorial diagram.
Below in conjunction with drawings and Examples the present invention is done further must the detailed description in detail.
Embodiment
Referring to accompanying drawing, Fig. 1 the present invention is based on the process flow sheet that plain paper prepares the SiC/Si bionic ceramic, comprise and to prepare ceramic paper in the impregnant sol behind the sheet trimming, then the oven dry, coating Bionic Design, add resin Si slurry, curing molding, charing, sintering and row's silicon obtain the SiC/Si bionic ceramic at last.Fig. 2 is the SEM photo of untreated plain paper; Fig. 3 is the SEM photo of the ceramic paper handled through silicon sol; Fig. 4 is the stereoscan photograph in the porous carbon sample transverse section after the charing; Fig. 5 is the stereoscan photograph after the local amplification of the section of SiC/Si multilayer tubular composite ceramics; Fig. 6 is a SiC/Si multilayer tubular composite ceramics pictorial diagram.
It below is the specific embodiment that the contriver provides.Need to prove, below be the more excellent example of the present invention, is used to explain the present invention, is not to limit the present invention with these embodiment.Those skilled in the art should recognize under the situation that does not break away from given technical characterictic of technical solution of the present invention and scope, and the increase that technical characterictic is done or replace with some same contents of this area all should belong to protection scope of the present invention.
Embodiment 1:
1) preparation of ceramic paper: dehydrated alcohol, tetraethoxy and distilled water is in the ratio of 2:1:0.8, prehydrolysis 1 hour.Regulating the pH value with strong aqua is 9, and under the stirring of induction stirring instrument, hydrolysis obtained silicon sol in 4 hours.Common paper was soaked 40 minutes in the silicon sol for preparing, oven dry, ceramic paper is made in paper weightening finish 55%～60%.
2) Bionic Design: resol is diluted to 40% concentration, and the silica flour that is 10 μ m according to ratio and the median size of 1:2 is mixed with slurry, and slurry evenly is coated on the ceramic paper.Carry out Bionic Design (tubulose sample), 120 ℃ of oven dry in following 2-4 hour, curing molding.
3) charing: the premolding sample is placed in the carbon-tube oven, at N
2Under the gas shiled, be heated to 800 ℃, insulation 1h with the heat-up rate of 1 ℃/min.Voltage with stove is adjusted to 0V then, allows the sample furnace cooling, closes stove when temperature is reduced to 300 ℃ and stops for N
2Gas, described N
2Gas is the technical pure ordinary nitrogen.
4) sintering: the paper carbon pipe after the charing is put into plumbago crucible, then crucible is put into vacuum resistance furnace, vacuumize 40min after, stop to vacuumize after being heated to 800 ℃ with 5 ℃/min heat-up rate, feed N again
2Gas also continues to be heated to about 1550 ℃ with 2 ℃/min heat-up rate, insulation 20min;
5) row's silicon: vacuumize once more after the insulation, and be warming up to about 1650 ℃, insulation 20min is adjusted to 0V with vacuum oven voltage, is cooled to 1200 ℃, closes vacuum pump, naturally cools to 900 ℃ of outages with stove and closes stove, promptly makes the SiC/Si tubular composite ceramic after the cooling.
Embodiment 2:
1) preparation of ceramic paper: dehydrated alcohol, tetraethoxy and distilled water is in the ratio of 2:1:0.8, prehydrolysis 1 hour.Regulating the pH value with strong aqua is 10, and under the stirring of induction stirring instrument, hydrolysis obtained silicon sol in 4 hours.Common paper was soaked 40 minutes in the silicon sol for preparing, oven dry, ceramic paper is made in paper weightening finish 55%～60%.
2) Bionic Design: resol is diluted to 30% concentration, and the silica flour that is 10 μ m according to ratio and the median size of 1:2 is mixed with slurry, and slurry evenly is coated on the ceramic paper.Carry out Bionic Design (tubulose sample), 120 ℃ of oven dry in following 2-4 hour, curing molding.
3) charing: the premolding sample is placed in the carbon-tube oven, at N
2Under the gas shiled, be heated to 800 ℃, insulation 1h with the heat-up rate of 1 ℃/min.Voltage with stove is adjusted to 0V then, allows the sample furnace cooling, closes stove when temperature is reduced to 300 ℃ and stops for N
2Gas, described N
2Gas is the technical pure ordinary nitrogen.
4) sintering: the paper carbon pipe after the charing is put into plumbago crucible, then crucible is put into vacuum resistance furnace, vacuumize 40min after, stop to vacuumize after being heated to 800 ℃ with 5 ℃/min heat-up rate, feed N again
2Gas also continues to be heated to about 1550 ℃ with 2 ℃/min heat-up rate, insulation 20min.
5) row's silicon: vacuumize once more after the insulation, and be warming up to about 1650 ℃, insulation 40min is adjusted to 0V with vacuum oven voltage, is cooled to 1200 ℃, closes vacuum pump, naturally cools to 900 ℃ of outages with stove and closes stove, promptly makes the SiC/Si tubular composite ceramic after the cooling.
Embodiment 3:
1) preparation of ceramic paper: dehydrated alcohol, tetraethoxy and distilled water is in the ratio of 2:1:0.8, prehydrolysis 1 hour.Regulating the pH value with strong aqua is 11, and under the stirring of induction stirring instrument, hydrolysis obtained silicon sol in 4 hours.Common paper was soaked 40 minutes in the silicon sol for preparing, oven dry, ceramic paper is made in paper weightening finish 60%～65%.
2) Bionic Design: resol is diluted to 20% concentration, and the silica flour that is 10 μ m according to ratio and the median size of 1:2 is mixed with slurry, and slurry evenly is coated on the ceramic paper.Carry out Bionic Design (tubulose sample), 120 ℃ of oven dry in following 2-4 hour, curing molding.
3) charing: premolding tubulose sample is placed in the carbon-tube oven, at N
2Under the gas shiled, be heated to 800 ℃, insulation 1h with the heat-up rate of 1 ℃/min.Voltage with stove is adjusted to 0V then, allows the sample furnace cooling, closes stove when temperature is reduced to 300 ℃ and stops for N
2Gas, described N
2Gas is the technical pure ordinary nitrogen.
4) sintering: the paper carbon pipe after the charing is put into plumbago crucible, then crucible is put into vacuum resistance furnace, vacuumize 40min after, stop to vacuumize after being heated to 800 ℃ with 5 ℃/min heat-up rate, feed N again
2Gas also continues to be heated to 1550 ℃ ± 10 ℃ with 2 ℃/min heat-up rate, insulation 60min;
5) row's silicon: vacuumize once more after the insulation, and be warming up to about 1650 ℃, insulation 30min is adjusted to 0V with vacuum oven voltage, is cooled to 1200 ℃, closes vacuum pump, naturally cools to 900 ℃ of outages with stove and closes stove, promptly makes the SiC/Si tubular composite ceramic after the cooling.
Embodiment 4:
1) preparation of ceramic paper: dehydrated alcohol, tetraethoxy and distilled water is in the ratio of 2:1:0.8, prehydrolysis 1 hour.Regulating the pH value with strong aqua is 11, and under the stirring of induction stirring instrument, hydrolysis obtained silicon sol in 4 hours.Common paper was soaked 40 minutes in the silicon sol for preparing, oven dry, ceramic paper is made in paper weightening finish 55%～60%.
2) Bionic Design: resol is diluted to 40% concentration, and the silica flour that is 10 μ m according to ratio and the median size of 1:2 is mixed with slurry, and slurry evenly is coated on the ceramic paper.Carry out Bionic Design (tubulose sample), 120 ℃ of oven dry in following 2-4 hour, curing molding.
3) charing: premolding tubulose sample is placed in the carbon-tube oven, at N
2Under the gas shiled, be heated to 800 ℃, insulation 1h with the heat-up rate of 1 ℃/min.Voltage with stove is adjusted to 0V then, allows the sample furnace cooling, closes stove when temperature is reduced to 300 ℃ and stops for N
2Gas, described N
2Gas is the technical pure ordinary nitrogen.
4) sintering: the paper carbon pipe after the charing is put into plumbago crucible, then crucible is put into vacuum resistance furnace, vacuumize 40min after, stop to vacuumize after being heated to 800 ℃ with 5 ℃/min heat-up rate, feed N again
2Gas also continues to be heated to about 1550 ℃ with 2 ℃/min heat-up rate, insulation 80min;
5) row's silicon: vacuumize once more after the insulation, and be warming up to about 1650 ℃, insulation 30min is adjusted to 0V with vacuum oven voltage, is cooled to 1200 ℃, closes vacuum pump, naturally cools to 900 ℃ of outages with stove and closes stove, promptly makes the SiC/Si tubular composite ceramic after the cooling.
Table 1:SiC/Si tubular ceramic composite materials property
| Sample | Density (g/cm 3) | Void content (%) | Flexural strength (Mpa) |
| Embodiment 1 | 2.11 | 19.5 | 163 |
| |
2.38 | 13.4 | 186 |
| Embodiment 3 | 2.43 | 11.1 | 200 |
| Embodiment 4 | 2.70 | 7.5 | 205 |
Claims (2)
1. the preparation method of a SiC/Si tubular composite ceramic is characterized in that, comprises the steps:
A, silicon sol preparation: with dehydrated alcohol, tetraethoxy and distilled water ratio in 2:1:0.8, prehydrolysis 1 hour, regulating the pH value with strong aqua is 9～11, under the stirring of induction stirring instrument, hydrolysis 2-6 hour, obtains silicon sol;
B, ceramic paper preparation: plain paper was soaked 40 minutes in the silicon sol for preparing, and oven dry makes paper weightening finish 55%～65%, makes ceramic paper;
C, tubulose specimen preparation: resol is diluted to 20%-40% concentration, and the silica flour that is 10 μ m according to ratio and the median size of 1:2 is mixed with slurry, evenly is coated on the ceramic paper; Make the multilayer tubular sample by Bionic Design, dried curing molding 2-4 hour down for 120 ℃;
D, charing: preformed multilayer tubular sample is placed in the carbon-tube oven, at N
2Under the gas shiled, be heated to 800 ℃ with the heat-up rate of 1 ℃/min, insulation 1h obtains paper carbon pipe;
E, sintering: the paper carbon pipe after the charing is put into plumbago crucible, then crucible is put into vacuum resistance furnace, vacuumize 40min after, stop to vacuumize after being heated to 800 ℃ with 5 ℃/min heat-up rate, feed N again
2Gas also continues to be heated to 1550 ℃ ± 10 ℃ with 2 ℃/min heat-up rate, is incubated 20 minutes～80 minutes;
F, row's silicon: vacuumize once more after the insulation, and be warming up to 1650 ℃ ± 10 ℃, be incubated 20 minutes～40 minutes, promptly make the SiC/Si tubular composite ceramic after the cooling.
2. the method for claim 1, it is characterized in that: the paper that adopts described in the step b is common printer paper, old newspaper, carton paper or kraft paper, paper sheet thickness is 0.1mm～0.3mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100176314A CN100462333C (en) | 2007-04-06 | 2007-04-06 | Method of preparing SiC base multilayer tubular composite ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100176314A CN100462333C (en) | 2007-04-06 | 2007-04-06 | Method of preparing SiC base multilayer tubular composite ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101058512A CN101058512A (en) | 2007-10-24 |
| CN100462333C true CN100462333C (en) | 2009-02-18 |
Family
ID=38864837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100176314A Expired - Fee Related CN100462333C (en) | 2007-04-06 | 2007-04-06 | Method of preparing SiC base multilayer tubular composite ceramic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100462333C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580390B (en) * | 2008-05-15 | 2012-10-03 | 中国科学院金属研究所 | Preparation method of silicon carbide ceramic tubular product |
| CN102190461A (en) * | 2010-03-16 | 2011-09-21 | 广东工业大学 | Protective coating capable of resisting fused alusil alloy corrosion in solar thermal power generation and preparation method thereof |
| CN101817682B (en) * | 2010-04-30 | 2012-05-30 | 郑州大学 | Preparation method of SiC-B4C composite thermoelectric material |
| CN102502642A (en) * | 2011-11-02 | 2012-06-20 | 桂林理工大学 | Method for preparing nanometer silicon carbide fiber in phenolic resin atmosphere |
| CN102538451A (en) * | 2011-12-22 | 2012-07-04 | 上海泛联科技股份有限公司 | Sintering device and method for preparing long-tube shaped structural ceramic continuously |
| CN103753898A (en) * | 2012-02-10 | 2014-04-30 | 廖树汉 | Sawable, drillable and unbreakable foam ceramic plate of several meters width with good thermal insulation performance capable of replacing steel plate |
| CN103242028B (en) * | 2012-02-10 | 2015-12-16 | 廖树汉 | Wide several meters thin 0.3 millimeter replacement steel plate can be sawed to bore and break not rotten trough-type ceramic cardboard |
| CN103755354B (en) * | 2012-02-10 | 2016-02-17 | 廖树汉 | Wide several meters thin 0.3 millimeter replacement steel plate can be sawed to bore and break not rotten sine wave pottery cardboard |
| CN103755355B (en) * | 2012-02-10 | 2016-02-24 | 廖树汉 | Wide several meters thin 0.3 millimeter replacement steel plate can be sawed to bore and break not rotten square wave pottery cardboard |
| CN107337468A (en) * | 2016-12-23 | 2017-11-10 | 辽宁卓异新材料有限公司 | A kind of preparation method and application of foamed ceramics porous burner medium |
| CN108892512A (en) * | 2018-09-07 | 2018-11-27 | 哈尔滨工业大学 | A method of silicon carbide is prepared using waste paper |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887794A (en) * | 2006-07-13 | 2007-01-03 | 西安交通大学 | Prepn process of laminated SiC-base composite ceramic |
-
2007
- 2007-04-06 CN CNB2007100176314A patent/CN100462333C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887794A (en) * | 2006-07-13 | 2007-01-03 | 西安交通大学 | Prepn process of laminated SiC-base composite ceramic |
Non-Patent Citations (4)
| Title |
|---|
| 纸制备SiC/Si层状陶瓷复合材料的微观结构和性能. 李冬云等.陶瓷学报，第27卷第1期. 2006 |
| 纸制备SiC/Si层状陶瓷复合材料的微观结构和性能. 李冬云等.陶瓷学报，第27卷第1期. 2006 * |
| 纸叠层设计制备SiC/Si层状陶瓷研究. 李冬云等.浙江大学学报（工学版），第40卷第8期. 2006 |
| 纸叠层设计制备SiC/Si层状陶瓷研究. 李冬云等.浙江大学学报（工学版），第40卷第8期. 2006 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101058512A (en) | 2007-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100462333C (en) | Method of preparing SiC base multilayer tubular composite ceramic | |
| US5250242A (en) | Method of producing ceramic sintered body having dense ceramic membrane | |
| JP5322382B2 (en) | Ceramic composite member and manufacturing method thereof | |
| US8048544B2 (en) | Ceramics made of preceramic paper or board structures, method of producing the same and use thereof | |
| CN106518089A (en) | Preparation method of high performance large size silicon nitride ceramic material | |
| CN104057667B (en) | A kind of TiAl/Ti 3siC 2composite board and preparation method thereof | |
| CN109704781A (en) | A kind of silicon nitride nano band aeroge and preparation method thereof | |
| CN105819882B (en) | A kind of ceramet composite substrate and its preparation process | |
| CN102191398A (en) | Preparation method of carborundum particle reinforced aluminum matrix composite material with high volume fraction | |
| KR20120025396A (en) | Setter for firing | |
| CN108484173B (en) | SiCf/SiC composite material and preparation method thereof | |
| CN104139572B (en) | A kind of charcoal/pottery-graphite composite material preparation technology and goods thereof | |
| CN101181798A (en) | Multi-gradient porous ceramic mold for ceramic injection forming and making method | |
| CN103264542A (en) | Titanium aluminum-ceramic layered material and preparation method thereof | |
| CN108863396B (en) | Silicon nitride-based continuous functional gradient ceramic ball and preparation method and application thereof | |
| CN105481477A (en) | Preparation method of graphite/SiC composite material | |
| CN100364926C (en) | Prepn process of laminated SiC-base composite ceramic | |
| CN115231936B (en) | Composite heat insulation material and preparation method thereof | |
| CN114014678B (en) | Quartz fiber/carbon fiber reinforced carbon-based composite flat plate and preparation method thereof | |
| CN113981732B (en) | Alumina/zirconia fiber composite heat-insulating material and preparation method thereof | |
| CN100515992C (en) | Method for preparing SiC/BN layered composite ceramic | |
| CN1970503A (en) | Metal/ ceramic laser sintering product post-processing method | |
| Song et al. | Effects of silicon particle size on microstructure and permeability of silicon-bonded SiC ceramics | |
| CN114685169A (en) | Preparation method of fiber-reinforced silicon carbide ceramic matrix composite based on slurry lamination design | |
| CN113896560A (en) | Preparation method of low-density porous heat-insulating material for industrial furnace |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090218 Termination date: 20130406 |