CN102061431A - Tungsten-copper composite material and preparation method thereof - Google Patents
Tungsten-copper composite material and preparation method thereof Download PDFInfo
- Publication number
- CN102061431A CN102061431A CN2010105931139A CN201010593113A CN102061431A CN 102061431 A CN102061431 A CN 102061431A CN 2010105931139 A CN2010105931139 A CN 2010105931139A CN 201010593113 A CN201010593113 A CN 201010593113A CN 102061431 A CN102061431 A CN 102061431A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- copper
- knitted body
- preparation
- composite material
- 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.)
- Granted
Links
Abstract
The invention relates to a tungsten-copper composite material, wherein tungsten and copper are mutually clad and through, and the tungsten-copper composite material comprises the following components in percentage by weight: 60-90 percent of tungsten and the balance of copper. A preparation method of the tungsten-copper composite material comprises the following steps of: washing a tungsten filament with acid, cleaning, and carrying out three-dimensional or two-dimensional braiding to obtain a tungsten filament braided body; placing a copper material into a graphite container, placing the obtained tungsten filament braided body on the copper material, and holding a temperature of 1200-1350 DEG C for 0.5-2h under a vacuum environment with the vacuum degree being larger than 1*10<-3>Pa; cooling to the room temperature in a furnace, and then removing redundant copper from the surface of the obtained green body to obtain the tungsten-copper composite material. The tungsten-copper composite material prepared with the preparation method has the advantages of avoiding the problem of nonuniform texture caused by nonuniform mixing of tungsten and copper alloy prepared by applying a traditional process.
Description
Technical field
The invention belongs to metallurgical technology field, relate to the preparation technology of matrix material, especially a kind of copper composite tungsten material and preparation method thereof.
Background technology
Tungsten-copper composite material has high rigidity, the low-expansion coefficient of tungsten concurrently, the electric-conductivity heat-conductivity high that copper is arranged again, its heat conduction, conductivity and thermal expansivity can be designed by adjustment tungsten, copper component concentration, therefore are widely used in wide spectrums such as microwave device, unicircuit packaged material, contact material.
The technical matters of preparation tungsten-copper composite material has two kinds of methods such as infiltration method, liquid phase activated sintering method usually.
Infiltration method: tungsten powder or the mixed powder that mixes the part copper powder are pressed into briquet, on briquet, place required copper powder (briquetting) then, the copper fusing is penetrated in the hole of pressed compact, form Tungsten-copper Composites.The advantage of this technological method is that the hole in the tungsten powder pressed compact can be filled by copper substantially, and resistance to air loss is better, and shortcoming is that product size changes greatly, and precision is low, needs to reserve more process redundancy, and not only efficient is low, and waste of raw materials is bigger, the manufacturing cost height.In addition, this technological method is difficult to obtain the tungsten-copper alloy of tungsten copper element homodisperse, mutual parcel.
Liquid phase activated sintering method: this method adopts conventional powder metallurgical technique, promptly mixes powder, compacting and sintering.In order to reduce sintering temperature, in pressed compact, added sintering aids such as micro-for example nickel, cobalt, cupric oxide, thereby reached the effect that reduces sintering temperature.The advantage of this technology is that the dimensional precision of sintered piece is higher, shortcoming is to have introduced unwanted alloying element in the alloy, has reduced the thermal conductivity of alloy, in addition, can there be micropore in the tungsten-copper alloy part that this technological method prepares, so resistance to air loss and thermal conductivity all are lower than infiltration method.
Except above-mentioned some limitation or the shortcoming of mentioning, also there are some common defectives in above-mentioned two kinds of technological methods: (1) powder batch mixing and sintering process are difficult to avoid fully pollute, make that foreign matter contents such as total oxygen in the alloy, nitrogen are higher, hindered its application at high vacuum environment; (2) distributing homogeneity of tungsten is difficult to be guaranteed in the alloy.
The present invention has overcome above-mentioned defective.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, provide that a kind of foreign matter content is low, density is high, tungsten and copper coats mutually, the tungsten-copper composite material and the preparation method of communicating structure mutually.
The present invention solves the problems of the technologies described above the technical scheme of being taked: a kind of copper composite tungsten material, and copper and tungsten coat mutually, connect, and wherein, the content of described tungsten is 60%～90% according to weight percent, and all the other are copper.
Mass percentage content for above-mentioned tungsten can be 60,61,62,63,64,65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89 or 90%.
Preparation method at above-mentioned tungsten-copper composite material comprises the steps:
Step 1 is that the tungsten filament of 0.1～100 μ m carries out carrying out three-dimensional or control of two-dimensional braided after pickling and the cleaning with diameter, obtains the tungsten filament knitted body;
Step 2 is positioned over copper material in the crystal vessel, the tungsten filament knitted body that obtains is positioned on the copper material, in vacuum tightness greater than 1 * 10
-3Under the vacuum environment of Pa, under 1200～1350 ℃ of temperature, be incubated 0.5～2 hour;
Step 3, cool to room temperature with the furnace after, copper that gained tungsten-copper alloy billet surface is unnecessary is removed, and promptly makes tungsten-copper composite material.
On the basis of such scheme, the weight of copper material is to need 105 ~ 110% of weight of copper according to filling tungsten filament knitted body hole in the described step 2.
On the basis of such scheme, the porosity of tungsten knitted body is 17,18,19 or 20% in the above-mentioned steps one, and the weight of copper material is to need 105,106,107,108,109 or 110% of weight of copper according to filling tungsten filament knitted body hole in the step 2.
On the basis of such scheme, the preparation method comprises the steps:
Step 1, selecting diameter for use is the tungsten filament of 15 μ m, behind 15% chlorohydric acid pickling, dries after the water flushing; Adopt the fibrage machine that tungsten filament is carried out 3 D weaving, control braiding parameter, the apparent density that makes the knitted body that obtains is 15.5～16.0 g/cm
3, this moment, the porosity of tungsten knitted body was 17～20%;
Step 2, calculate the weight of the required copper of complete filling gained tungsten knitted body hole, the copper ingot of calculated weight 110% is put into crystal vessel, again the tungsten filament knitted body is positioned over the copper ingot top, then crystal vessel is placed vacuum oven, keep the interior vacuum tightness of stove 1 * 10
-3More than the Pa, heat temperature raising speed is 3～10 ℃/minute, and infiltrating temperature is 1300 ℃, and soaking time is 1.5 hours;
Step 3 cools to room temperature with the furnace, after the taking-up, removes the unnecessary copper of Tungsten-copper Composites billet surface, promptly makes tungsten-copper composite material.
On the basis of such scheme, the preparation method also can be by following step:
Step 1, selecting diameter for use is the tungsten filament of 25 μ m, behind 15% chlorohydric acid pickling, dries after the water flushing, adopts the fibrage machine that tungsten filament is carried out 3 D weaving then, control braiding parameter, the apparent density that makes the knitted body that obtains is 11.5～12.0 g/cm
3, the porosity of tungsten knitted body is 38～40% at this moment;
Step 2, calculate the weight of the required copper of complete filling gained tungsten knitted body hole, the copper ingot of calculated weight 105% is put into crystal vessel, again the tungsten filament knitted body is positioned over the copper ingot top, then crystal vessel is placed vacuum oven, keep the interior vacuum tightness of stove 1 * 10
-3More than the Pa, heat temperature raising speed is 3～10 ℃/minute, and infiltrating temperature is 1200 ℃, and soaking time is 2 hours;
Step 3 cools to room temperature with the furnace, after the taking-up, removes the unnecessary copper of Tungsten-copper Composites billet surface, promptly makes tungsten-copper composite material.
Because the basketry parameter that control is different, just can obtain the pre-knitted body of different porosities, this moment tungsten preprogrammed body apparent density to have only 40～80%(of theoretical density be that the porosity of tungsten knitted body is 20～60%), be 10cm with the 105～110%(that oozes the copper amount of porosity correspondence such as a volume more then
3, porosity is 30% preprogrammed body, it is 26.7g that original required theory is oozed the copper amount, and the copper amount of oozing during preparation is 29.3g), just obtain fine and close Tungsten-copper Composites after infiltration is filled.
With respect to prior art, the present invention has the following advantages:
The hole of the tungsten filament knitted body that the present invention is prepared connects, and in a vacuum, fused copper liquid is very easy to be filled in the hole, and the tungsten-copper alloy of gained has the high-compactness that approaches theoretical density; The even phenomenon of the tissue odds that the tungsten-copper alloy of having avoided traditional technology to prepare causes because of batch mixing is inhomogeneous; The composition variation range that the tungsten-copper alloy of the present invention's preparation allows is big, in this scope, and the structure that tungsten in the alloy and copper can both form mutual coating, connect mutually; Because the infiltration process is carried out under high vacuum condition, the oxygen level and the foreign matter content of prepared tungsten-copper alloy are lower.
Embodiment
Below in conjunction with two specific embodiments, the present invention is further understood in exemplary illustration and help.But the embodiment detail only is for the present invention is described, does not represent the whole technical schemes of the present invention under conceiving, and therefore should not be construed as the qualification to technical scheme of the present invention.Some do not depart from the unsubstantiality of the present invention's design changes, and for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to rights protection scope of the present invention.
Embodiment 1
A kind of tungsten-copper alloy comprises following component and content (weight percent): tungsten 90%, copper 10%.The preparation method may further comprise the steps:
Step 1, selecting diameter for use is the tungsten filament of 15 μ m, behind 15% chlorohydric acid pickling, dries after the water flushing; Adopt the fibrage machine that tungsten filament is carried out 3 D weaving, control braiding parameter, make the knitted body that obtains porosity be 17～20%, this moment, tungsten knitted body apparent density was 15.5～16.0 g/cm
3
Step 2 is calculated the weight of the required copper of complete filling gained tungsten knitted body hole, and the copper ingot of calculated weight 110% is put into crystal vessel, the tungsten filament knitted body is positioned over the copper ingot top again.Crystal vessel is placed vacuum oven, keep the interior vacuum tightness of stove 1 * 10
-3More than the Pa, heat temperature raising speed is 3～10 ℃/minute, and infiltrating temperature is 1300 ℃, and soaking time is 1.5 hours;
Step 3 cools to room temperature with the furnace, after the taking-up, removes the unnecessary copper of Tungsten-copper Composites billet surface, promptly makes tungsten-copper composite material.
Embodiment 2
A kind of tungsten-copper alloy comprises following component and content (weight percent): tungsten 75%, copper 25%.Preparation technology may further comprise the steps:
Step 1, selecting diameter for use is the tungsten filament of 25 μ m, behind 15% chlorohydric acid pickling, dry after the water flushing, adopt the fibrage machine that tungsten filament is carried out 3 D weaving then, control braiding parameter, the porosity that makes the knitted body that obtains is 38～40%, this moment, the apparent density of tungsten knitted body was 11.5～12.0g/cm
3
Step 2 is calculated the weight of the required copper of complete filling gained tungsten knitted body hole, and the copper ingot of calculated weight 105% is put into crystal vessel, the tungsten filament knitted body is positioned over the copper ingot top again.Crystal vessel is placed vacuum oven, keep the interior vacuum tightness of stove 1 * 10
-3More than the Pa, heat temperature raising speed is 3～10 ℃/minute, and infiltrating temperature is 1200 ℃, and soaking time is 2 hours;
Step 3 cools to room temperature with the furnace, after the taking-up, removes the unnecessary copper of Tungsten-copper Composites billet surface, promptly makes tungsten-copper composite material.
Claims (5)
1. copper composite tungsten material, copper and tungsten coat mutually, connect, and it is characterized in that the content according to weight percent tungsten is 60%-90%, and all the other are copper.
2. the preparation method of a tungsten-copper composite material is characterized in that the preparation method comprises the steps:
Step 1 is that the tungsten filament of 0.1 ~ 100 μ m carries out carrying out three-dimensional or control of two-dimensional braided after pickling and the cleaning with diameter, obtains the tungsten filament knitted body;
Step 2 is positioned over copper material in the crystal vessel, the tungsten filament knitted body that obtains is positioned on the copper material, in vacuum tightness greater than 1 * 10
-3Under the vacuum environment of Pa, under 1200 ~ 1350 ℃ of temperature, be incubated 0.5 ~ 2 hour;
Step 3, cool to room temperature with the furnace after, copper that gained tungsten-copper alloy billet surface is unnecessary is removed, and promptly makes tungsten-copper composite material.
3. according to the preparation method of the described tungsten-copper composite material of claim 2, it is characterized in that:
The weight of copper material is to need 105 ~ 110% of weight of copper according to filling tungsten filament knitted body hole in the step 2.
4. according to the preparation method of claim 2 or 3 described tungsten-copper alloys, it is characterized in that the preparation method comprises the steps:
Step 1, selecting diameter for use is the tungsten filament of 15 μ m, behind 15% chlorohydric acid pickling, dries after the water flushing; Adopt the fibrage machine that tungsten filament is carried out 3 D weaving, control braiding parameter, the apparent density that makes the knitted body that obtains is 15.5-16.0 g/cm
3, this moment, the porosity of tungsten knitted body was 17-20%;
Step 2, calculate the weight of the required copper of complete filling gained tungsten knitted body hole, the copper ingot of calculated weight 110% is put into crystal vessel, again the tungsten filament knitted body is positioned over the copper ingot top, then crystal vessel is placed vacuum oven, keep the interior vacuum tightness of stove 1 * 10
-3More than the Pa, heat temperature raising speed is 3 ~ 10 ℃/minute, and infiltrating temperature is 1300 ℃, and soaking time is 1.5 hours;
Step 3 cools to room temperature with the furnace, after the taking-up, removes the unnecessary copper of Tungsten-copper Composites billet surface, promptly makes tungsten-copper composite material.
5. according to the preparation method of claim 2 or 3 described tungsten-copper alloys, it is characterized in that the preparation method comprises the steps:
Step 1, selecting diameter for use is the tungsten filament of 25 μ m, behind 15% chlorohydric acid pickling, dries after the water flushing, adopts the fibrage machine that tungsten filament is carried out 3 D weaving then, control braiding parameter, the apparent density that makes the knitted body that obtains is 11.5-12.0 g/cm
3, the porosity of tungsten knitted body is at 38-40% at this moment;
Step 2, calculate the weight of the required copper of complete filling gained tungsten knitted body hole, the copper ingot of calculated weight 105% is put into crystal vessel, again the tungsten filament knitted body is positioned over the copper ingot top, then crystal vessel is placed vacuum oven, keep the interior vacuum tightness of stove 1 * 10
-3More than the Pa, heat temperature raising speed is 3 ~ 10 ℃/minute, and infiltrating temperature is 1200 ℃, and soaking time is 2 hours;
Step 3 cools to room temperature with the furnace, after the taking-up, removes the unnecessary copper of Tungsten-copper Composites billet surface, promptly makes tungsten-copper composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010593113 CN102061431B (en) | 2010-12-17 | 2010-12-17 | Tungsten-copper composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010593113 CN102061431B (en) | 2010-12-17 | 2010-12-17 | Tungsten-copper composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102061431A true CN102061431A (en) | 2011-05-18 |
| CN102061431B CN102061431B (en) | 2013-04-03 |
Family
ID=43996935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010593113 Expired - Fee Related CN102061431B (en) | 2010-12-17 | 2010-12-17 | Tungsten-copper composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102061431B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925727A (en) * | 2012-11-14 | 2013-02-13 | 武汉理工大学 | Preparation method for high-performance Zn@W-Cu heat composite |
| CN103451579A (en) * | 2013-09-30 | 2013-12-18 | 上海工程技术大学 | Method for preparing molybdenum copper composite materials with fiber structures |
| CN105039876A (en) * | 2015-07-06 | 2015-11-11 | 西安理工大学 | Preparation method for W-Cu composite materials of fiber and particle hybrid structure |
| CN107052350A (en) * | 2017-06-16 | 2017-08-18 | 大连理工大学 | A kind of method for connecting tungsten material and copper material |
| CN107739862A (en) * | 2017-10-24 | 2018-02-27 | 宝鸡市铭坤有色金属有限公司 | A kind of preparation method of tungsten-copper alloy material |
| CN110064899A (en) * | 2019-05-06 | 2019-07-30 | 福达合金材料股份有限公司 | A kind of tungsten answers copper contact material and preparation method thereof |
| CN112301297A (en) * | 2019-07-24 | 2021-02-02 | 中国科学院金属研究所 | Copper-based composite material reinforced by continuous tungsten fiber braid and preparation method thereof |
| CN113088838A (en) * | 2021-04-02 | 2021-07-09 | 中国科学院合肥物质科学研究院 | Tungsten copper sheet component with tungsten fiber net reinforcing copper base composite layer |
| CN114592161A (en) * | 2020-12-03 | 2022-06-07 | 厦门虹鹭钨钼工业有限公司 | Preparation method of clad metal tungsten wire |
| CN114657481A (en) * | 2022-03-08 | 2022-06-24 | 厦门欧斯拓科技有限公司 | Preparation method of rare earth composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3438753A (en) * | 1965-07-23 | 1969-04-15 | Mallory & Co Inc P R | Tungsten-copper composites |
| JPH10265887A (en) * | 1997-03-27 | 1998-10-06 | Toshiba Corp | Sintering alloy material |
| CN1590571A (en) * | 2003-09-05 | 2005-03-09 | 上海材料研究所 | Tungsten copper functional composite material and its preparation technology |
| CN1651590A (en) * | 2005-02-03 | 2005-08-10 | 西安建筑科技大学 | Preparation technology of tungsten copper or tungsten silver composite material |
| CN101092669A (en) * | 2007-05-18 | 2007-12-26 | 西安建筑科技大学 | Method for preparing wolfram steel or composite material of tungsten and silver |
-
2010
- 2010-12-17 CN CN 201010593113 patent/CN102061431B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3438753A (en) * | 1965-07-23 | 1969-04-15 | Mallory & Co Inc P R | Tungsten-copper composites |
| JPH10265887A (en) * | 1997-03-27 | 1998-10-06 | Toshiba Corp | Sintering alloy material |
| CN1590571A (en) * | 2003-09-05 | 2005-03-09 | 上海材料研究所 | Tungsten copper functional composite material and its preparation technology |
| CN1651590A (en) * | 2005-02-03 | 2005-08-10 | 西安建筑科技大学 | Preparation technology of tungsten copper or tungsten silver composite material |
| CN101092669A (en) * | 2007-05-18 | 2007-12-26 | 西安建筑科技大学 | Method for preparing wolfram steel or composite material of tungsten and silver |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925727A (en) * | 2012-11-14 | 2013-02-13 | 武汉理工大学 | Preparation method for high-performance Zn@W-Cu heat composite |
| CN102925727B (en) * | 2012-11-14 | 2015-03-04 | 武汉理工大学 | Preparation method for high-performance Zn@W-Cu heat composite |
| CN103451579A (en) * | 2013-09-30 | 2013-12-18 | 上海工程技术大学 | Method for preparing molybdenum copper composite materials with fiber structures |
| CN105039876A (en) * | 2015-07-06 | 2015-11-11 | 西安理工大学 | Preparation method for W-Cu composite materials of fiber and particle hybrid structure |
| CN107052350A (en) * | 2017-06-16 | 2017-08-18 | 大连理工大学 | A kind of method for connecting tungsten material and copper material |
| CN107739862A (en) * | 2017-10-24 | 2018-02-27 | 宝鸡市铭坤有色金属有限公司 | A kind of preparation method of tungsten-copper alloy material |
| CN110064899A (en) * | 2019-05-06 | 2019-07-30 | 福达合金材料股份有限公司 | A kind of tungsten answers copper contact material and preparation method thereof |
| CN110064899B (en) * | 2019-05-06 | 2021-03-05 | 福达合金材料股份有限公司 | Tungsten-copper-clad electrical contact material and preparation method thereof |
| CN112301297A (en) * | 2019-07-24 | 2021-02-02 | 中国科学院金属研究所 | Copper-based composite material reinforced by continuous tungsten fiber braid and preparation method thereof |
| CN114592161A (en) * | 2020-12-03 | 2022-06-07 | 厦门虹鹭钨钼工业有限公司 | Preparation method of clad metal tungsten wire |
| CN113088838A (en) * | 2021-04-02 | 2021-07-09 | 中国科学院合肥物质科学研究院 | Tungsten copper sheet component with tungsten fiber net reinforcing copper base composite layer |
| CN113088838B (en) * | 2021-04-02 | 2021-12-10 | 中国科学院合肥物质科学研究院 | Tungsten copper sheet component with tungsten fiber net reinforcing copper base composite layer |
| CN114657481A (en) * | 2022-03-08 | 2022-06-24 | 厦门欧斯拓科技有限公司 | Preparation method of rare earth composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102061431B (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102061431B (en) | Tungsten-copper composite material and preparation method thereof | |
| CN105441884B (en) | A kind of preparation method of molybdenum niobium alloy sputtering target material | |
| JP2021031381A (en) | Method of preparing high-conductivity pantograph carbon contact strip | |
| CN102312129B (en) | Method for preparing titanium niobium zirconium tin biomedical titanium alloys by discharge plasma sintering | |
| CN101956148B (en) | Dual composite high strength and toughness block amorphous alloy and preparation method thereof | |
| CN108213408A (en) | A kind of method that the porous metal parts with labyrinth are prepared using 3D printing technique | |
| CN104630527A (en) | Method for preparing copper-based diamond composite material | |
| CN105169471A (en) | Implant porous niobium-titanium alloy material for medical use and preparation method of alloy material | |
| CN112974774B (en) | Silver-based composite material and preparation method thereof | |
| CN102492884A (en) | Preparation method of novel tungsten-copper-zinc alloy material | |
| CN101984104B (en) | Preparation method of biomedical bulk porous amorphous alloy | |
| CN104232995A (en) | High-toughness ultrafine-grain composite titanium alloy and application and preparation method thereof | |
| CN102795860A (en) | Method for preparing silicon nitride ceramic balls | |
| CN114525438B (en) | Tungsten copper composite material and preparation method thereof | |
| CN109047649B (en) | Graphite casting mold for improving titanium alloy casting mold filling performance and preparation method thereof | |
| CN106048355B (en) | The preparation method of Nb Si based ultra-high temperature alloy pigs | |
| CN105543535B (en) | Al4SiC4With Cr cooperative reinforcings net/spherical copper product and preparation method | |
| CN108774698A (en) | A kind of Aludirome plate and preparation method thereof | |
| CN104513953B (en) | The preparation method of molybdenum silicon target | |
| CN112620631A (en) | Method for preparing Mo-Cu alloy by field-assisted activation sintering | |
| Cai et al. | Electrical, thermal, and mechanical properties of Cu50Zr40Ti10 bulk amorphous composite | |
| CN101402137A (en) | Method for producing CuCr40 contact material with vacuum fusion cast method | |
| US20230117192A1 (en) | Preparation method for w-cu composite plate with cu phase in finger-shaped gradient distribution | |
| CN106086493A (en) | A kind of fast low temperature sinters the method preparing CuCr alloy material | |
| CN105731809A (en) | Insulating material for heating wire, preparation and application method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130403 Termination date: 20141217 |
|
| EXPY | Termination of patent right or utility model |