CN102371719B - Method for preparing copper/molybdenum/copper layered compound metallic material - Google Patents
Method for preparing copper/molybdenum/copper layered compound metallic material Download PDFInfo
- Publication number
- CN102371719B CN102371719B CN 201110250983 CN201110250983A CN102371719B CN 102371719 B CN102371719 B CN 102371719B CN 201110250983 CN201110250983 CN 201110250983 CN 201110250983 A CN201110250983 A CN 201110250983A CN 102371719 B CN102371719 B CN 102371719B
- Authority
- CN
- China
- Prior art keywords
- copper
- molybdenum
- plate
- copper coin
- composite
- 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
- Pressure Welding/Diffusion-Bonding (AREA)
- Metal Rolling (AREA)
Abstract
The invention discloses a method for preparing a copper/molybdenum/copper layered compound metallic material, which comprises the following steps of: 1) polishing to-be-compounded surfaces of a first copper plate, a second copper plate and a molybdenum plate; 2) explosively compounding the molybdenum plate with the first copper plate, thereby acquiring a compound plate; 3) annealing the compound plate; 4) explosively compounding the compound plate with the second copper plate, thereby acquiring a copper/molybdenum/copper compound plate slab; 5) performing hot-rolling on the copper/molybdenum/copper compound plate slab; and 6) annealing and cooling the compound plate slab along with a furnace, thereby acquiring the copper/molybdenum/copper layered compound metallic material. The method provided by the invention is simple; the demand on equipment is low; the production cost is low; the volume production is easily realized; and the method is higher in production application value. According to the method, an explosive compounding technique is used for realizing the copper/molybdenum compounding, thereby overcoming the processing difficulty in compounding copper and molybdenum. Rolling technical parameters are controlled, thereby avoiding the situations of cracked compound interface and broken molybdenum and supplying a powerful technical support for the volume production of the copper/molybdenum/copper layered compound metallic material.
Description
Technical field
The invention belongs to the laminar composite preparing technical field, be specifically related to a kind of copper/molybdenum/copper layered composite metal preparation methods.
Background technology
Copper/molybdenum/copper metallic composite possesses excellent heat, electrical property, uses as substrate, abaculus, connector and heat dissipation element in large scale integrated circuit and HIGH-POWERED MICROWAVES device.Its high heat conduction and hear resistance have greatly improved the function of use of microelectronic component, make device miniaturization; Its suitable thermal coefficient of expansion can be connected with semi-conducting material such as silicon, GaAs in the microelectronic component and the fine coupling of ceramic material, and the heat fatigue of avoiding thermal stress to cause is destroyed.
At present, the preparation method of copper/molybdenum/copper laminated-metal composite has following several:
(1) explosive welding composite algorithm, the high-strength chemical energy that produces by explosive charge drives compound plate high velocity impact substrate, the moment HTHP that the point of impingement produces has not only destroyed the oxide-film of metal surface, exposed fresh surface, and form the welding transition district that is similar to fluid and waveform metallurgical binding feature that one deck has plastic deformation, fusing, diffusion exposing fresh metal surface, realize the strong combination of different metal.
Can see copper and molybdenum not solid solution mutually on the copper molybdenum binary phase diagraml, both can not form true alloy, and the physical property of copper and molybdenum differs greatly, and conventional welding method can not make the copper molybdenum be soldered to together.The explosive welding composite algorithm just has the ability of the big metal of this class performance difference of soldering copper/molybdenum, but this method is fit to the production of bigger, the thick composite plate of individual area and slab, even can not directly produce for thinner composite plate.
(2) roll-bonding method, metallic plate apply under the pressure effect powerful on it being subjected to milling train, double layer of metal treat composite surface generation plastic deformation, surface metal-layer breaks.Subsequently, clean and metal level activation exposes from the metal surface of breaking, under the crunch effect, form plane metallurgical binding.Faying face continues to enlarge in follow-up heat treatment process, forms firm combination.
Rollingly compoundly must impose bigger initial reduction in pass, impel the physics contact of composite surface, for copper/molybdenum group concerning, bigger metal strain very easily makes molybdenum plate that fracture or slabbing take place.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned the deficiencies in the prior art, provide a kind of method simple, less demanding to equipment, production cost is low, realize easily producing in batches, have copper/molybdenum/copper layered composite metal preparation methods that production application preferably is worth.This method adopts the blast complex technique to realize the compound of copper/molybdenum, overcome copper/molybdenum and be difficult to a compound processing difficult problem, and the technological parameter by controlled rolling, avoided compound interface cracking and molybdenum itself that situation about rupturing takes place, for mass production copper/molybdenum/copper layered composite metal material provides strong technical support.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of copper/molybdenum/copper layered composite metal preparation methods is characterized in that this method may further comprise the steps:
Step 1, copper coin one and copper coin two treated that composite surface carries out grinding process to surface roughness with sand paper and is not more than 1.6 μ m, with molybdenum plate treat that composite surface carries out grinding process to surface roughness with emery wheel and is not more than 1.6 μ m, the copper coin one after the grinding process, copper coin two and molybdenum plate treated that composite surface is clean with alcohol wipe;
The material of clearance material one described in the above-mentioned steps two is identical with copper coin one, and the height of clearance material one is 1mm~5mm.
Explosive is ammonium nitrate-fuel oil mixture described in above-mentioned steps two and the step 4, and the laying density of explosive is 0.5g/cm
3~1.0g/cm
3, the laying of explosive highly is 15mm~40mm, and explosion velocity of explosive is 1500m/s~3000m/s.
The time of annealing in process described in the above-mentioned steps three is 0.5h~1h.
The material of clearance material two described in the above-mentioned steps four is identical with copper coin two, and the height of clearance material two is 1mm~5mm.
Described in the above-mentioned steps five in the course of hot rolling every time rolling temperature be not less than 500 ℃.
Pass deformation rate is not more than 10% described in the above-mentioned steps five.
The total deformation rate of hot rolling described in the above-mentioned steps five is 40%~85%.
The time of annealing in process described in the above-mentioned steps six is 0.5h~1h.
The present invention compared with prior art has the following advantages:
1, the inventive method is simple, and is less demanding to equipment, and production cost is low, realizes easily producing in batches, has production application preferably and is worth.
2, the present invention is by arranging rational gap, select suitable explosive property and explosive laying density and lay height, adopt the blast complex technique to realize the compound of copper/molybdenum at rigid foundation, overcome copper/molybdenum and be difficult to a compound processing difficult problem, and the technological parameter by controlled rolling, avoided compound interface cracking and molybdenum itself that the situation of fracture takes place, guaranteed that the layered composite metal material interface has certain bond strength, for mass production copper/molybdenum/copper layered composite metal material provides strong technical support.
3, copper plate thickness reduces about 70%~85% in the blast recombination process of the present invention, molybdenum plate thickness reduces about 60%~75%, can design each layer thickness of copper/molybdenum/copper layered composite metal material according to instructions for use, and the blanking thickness of definite copper coin, molybdenum plate, preparation has the copper/molybdenum/copper layered composite metal material of different thermoelectricity capabilities.
4, adopting the density of the copper/molybdenum/copper layered composite metal material of method preparation of the present invention is 9.15g/cm
3~9.8g/cm
3, coefficient of thermal expansion is 6.8 * 10
-6K
-1~10.0 * 10
-6K
-1, the plane thermal conductivity is 190W/mK~320W/mK.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is the compound structural representation of the embodiment of the invention 1 molybdenum plate and copper coin one blast.
Fig. 2 is the compound structural representation of the embodiment of the invention 1 composite plate and copper coin two blasts.
Description of reference numerals:
1-copper coin one; 2-molybdenum plate; 3-copper coin two;
4-clearance material one; 5-clearance material two; 6-composite plate.
The specific embodiment
Embodiment 1
Thickness is the preparation of copper/molybdenum/copper layered composite metal material of 0.3mm: 0.5mm: 0.3mm:
Step 1, copper coin 1 and copper coin 23 treated that composite surface carries out grinding process to surface roughness with sand paper and is not more than 1.6 μ m, with molybdenum plate 2 treat that composite surface carries out grinding process to surface roughness with emery wheel and is not more than 1.6 μ m, the copper coin 1 after the grinding process, copper coin 23 and molybdenum plate 2 treated that composite surface is clean with alcohol wipe; Described copper coin 1 and copper coin 23 trades mark are T2, and specification is 2mm * 110mm * 180mm, and the trade mark of described molybdenum plate 2 is Mo1, and specification is 2mm * 100mm * 150mm;
The density of the copper/molybdenum/copper layered composite metal material of present embodiment preparation is 9.4g/cm
3~9.6g/cm
3, coefficient of thermal expansion is 8.5 * 10
-6K
-1~8.9 * 10
-6K
-1, the plane thermal conductivity is 250W/mK~280W/mK.
Thickness is the preparation of copper/molybdenum/copper layered composite metal material of 0.2mm: 0.7mm: 0.2mm:
Step 1, copper coin 1 and copper coin 23 treated that composite surface carries out grinding process to surface roughness with sand paper and is not more than 1.6 μ m, with molybdenum plate 2 treat that composite surface carries out grinding process to surface roughness with emery wheel and is not more than 1.6 μ m, the copper coin 1 after the grinding process, copper coin 23 and molybdenum plate 2 treated that composite surface is clean with alcohol wipe; The trade mark of described copper coin 1 and copper coin 23 is T2, and specification is 2mm * 160mm * 230mm, and the trade mark of described molybdenum plate 2 is Mo1, and specification is 3mm * 150mm * 200mm;
The density of the copper/molybdenum/copper layered composite metal material of present embodiment preparation is 9.65g/cm
3~9.8g/cm
3, coefficient of thermal expansion is 6.8 * 10
-6K
-1~7.2 * 10
-6K
-1, the plane thermal conductivity is 190W/mK~220W/mK.
Thickness is the preparation of copper/molybdenum/copper layered composite metal material of 0.3mm: 0.2mm: 0.3mm:
Step 1, copper coin 1 and copper coin 23 treated that composite surface carries out grinding process to surface roughness with sand paper and is not more than 1.6 μ m, with molybdenum plate 2 treat that composite surface carries out grinding process to surface roughness with emery wheel and is not more than 1.6 μ m, the copper coin 1 after the grinding process, copper coin 23 and molybdenum plate 2 treated that composite surface is clean with alcohol wipe; The trade mark of described copper coin 1 and copper coin 23 is T2, and specification is 1mm * 110mm * 180mm, and the trade mark of molybdenum plate 2 is Mo1, and specification is 0.5mm * 100mm * 150mm;
The density of the copper/molybdenum/copper layered composite metal material of present embodiment preparation is 9.15g/cm
3~9.35g/cm
3, coefficient of thermal expansion is 9.6 * 10
-6K
-1~10 * 10
-6K
-1, the plane thermal conductivity is 290W/mK~320W/mK.
Thickness is the preparation of copper/molybdenum/copper layered composite metal material of 0.3mm: 0.4mm: 0.3mm:
Step 1, copper coin 1 and copper coin 23 treated that composite surface carries out grinding process to surface roughness with sand paper and is not more than 1.6 μ m, with molybdenum plate 2 treat that composite surface carries out grinding process to surface roughness with emery wheel and is not more than 1.6 μ m, the copper coin 1 after the grinding process, copper coin 23 and molybdenum plate 2 treated that composite surface is clean with alcohol wipe; The trade mark of described copper coin 1 and copper coin 23 is T2, and specification is 0.6mm * 110mm * 180mm, and the trade mark of molybdenum plate 2 is Mo1, and specification is 0.5mm * 100mm * 150mm;
The density of the copper/molybdenum/copper layered composite metal material of present embodiment preparation is 9.25g/cm
3~9.4g/cm
3, coefficient of thermal expansion is 8.9 * 10
-6K
-1~9.2 * 10
-6K
-1, the plane thermal conductivity is 270W/mK~290W/mK.
Thickness is the preparation of copper/molybdenum/copper layered composite metal material of 0.4mm: 0.4mm: 0.4mm:
Step 1, copper coin 1 and copper coin 23 treated that composite surface carries out grinding process to surface roughness with sand paper and is not more than 1.6 μ m, with molybdenum plate 2 treat that composite surface carries out grinding process to surface roughness with emery wheel and is not more than 1.6 μ m, the copper coin 1 after the grinding process, copper coin 23 and molybdenum plate 2 treated that composite surface is clean with alcohol wipe; The trade mark of described copper coin 1 and copper coin 23 is T2, and specification is 0.8mm * 110mm * 180mm, and the trade mark of molybdenum plate 2 is Mo1, and specification is 0.5mm * 100mm * 150mm;
The density of the copper/molybdenum/copper layered composite metal material of present embodiment preparation is 9.35g/cm
3~9.5g/cm
3, coefficient of thermal expansion is 6.9 * 10
-6K
-1~7.4 * 10
-6K
-1, the plane thermal conductivity is 220W/mK~250W/mK.
The above; it only is preferred embodiment of the present invention; be not that the present invention is done any restriction, every any simple modification, change and equivalent structure of above embodiment being done according to the invention technical spirit changes, and all still belongs in the protection domain of technical solution of the present invention.
Claims (8)
1. copper/molybdenum/copper layered composite metal preparation methods is characterized in that this method may further comprise the steps:
Step 1, copper coin one (1) and copper coin two (3) treated that composite surface carries out grinding process to surface roughness with sand paper and is not more than 1.6 μ m, with molybdenum plate (2) treat that composite surface carries out grinding process to surface roughness with emery wheel and is not more than 1.6 μ m, the copper coin one (1) after the grinding process, copper coin two (3) and molybdenum plate (2) treated that composite surface is clean with alcohol wipe;
Step 2, the molybdenum plate (2) of wiped clean in the step 1 is placed on the rigid foundation, in molybdenum plate (2) top clearance material one (4) is set evenly then, again copper coin one (1) is placed clearance material one (4) top, and keep copper coin one (1) treat that composite surface down, at last explosive is layed in copper coin one (1) top, it is compound by cap sensitive explosive molybdenum plate (2) and copper coin one (1) to be exploded, and obtains composite plate (6); The quantity of described clearance material one (4) is no less than two;
Step 3, be annealing in process 0.1h~3h under 500 ℃~950 ℃ the condition in temperature with composite plate described in the step 2 (6);
Step 4, will place on the rigid foundation through the composite plate after the annealing in process (6) in the step 3, and keep molybdenum plate last, in composite plate (6) top clearance material two (5) is set evenly then, again copper coin two (3) is placed clearance material two (5) tops, and keep copper coin two (3) treat that composite surface down, at last explosive is layed in copper coin two (3) top, it is compound by cap sensitive explosive composite plate (6) and copper coin two (3) to be exploded, and obtains copper/molybdenum/copper composite plate blanks; The quantity of described clearance material two (5) is no less than two;
Step 5, with copper/molybdenum described in the step 4/copper composite plate blanks in 500 ℃~780 ℃ hot rolling 3~8 passages, pass deformation rate is not more than 30%;
Step 6, with being annealing in process 0.1h~3h under 500 ℃~950 ℃ the condition in temperature through the copper/molybdenum after the hot rolling/copper composite plate blanks in the step 5, with obtaining copper/molybdenum/copper layered composite metal material after the stove cooling.
2. a kind of copper/molybdenum according to claim 1/copper layered composite metal preparation methods is characterized in that, the material of clearance material described in the step 2 one (4) is identical with copper coin one (1), and the height of clearance material one (4) is 1mm~5mm.
3. a kind of copper/molybdenum according to claim 1/copper layered composite metal preparation methods is characterized in that explosive is ammonium nitrate-fuel oil mixture described in step 2 and the step 4, and the laying density of explosive is 0.5g/cm
3~1.0g/cm
3, the laying of explosive highly is 15mm~40mm, and explosion velocity of explosive is 1500m/s~3000m/s.
4. a kind of copper/molybdenum according to claim 1/copper layered composite metal preparation methods is characterized in that, the time of annealing in process described in the step 3 is 0.5h~1h.
5. a kind of copper/molybdenum according to claim 1/copper layered composite metal preparation methods is characterized in that, the material of clearance material described in the step 4 two (5) is identical with copper coin two (3), and the height of clearance material two (5) is 1mm~5mm.
6. a kind of copper/molybdenum according to claim 1/copper layered composite metal preparation methods is characterized in that pass deformation rate is not more than 10% described in the step 5.
7. a kind of copper/molybdenum according to claim 1/copper layered composite metal preparation methods is characterized in that, the total deformation rate of hot rolling described in the step 5 is 40%~85%.
8. a kind of copper/molybdenum according to claim 1/copper layered composite metal preparation methods is characterized in that, the time of annealing in process described in the step 6 is 0.5h~1h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110250983 CN102371719B (en) | 2011-08-29 | 2011-08-29 | Method for preparing copper/molybdenum/copper layered compound metallic material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110250983 CN102371719B (en) | 2011-08-29 | 2011-08-29 | Method for preparing copper/molybdenum/copper layered compound metallic material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102371719A CN102371719A (en) | 2012-03-14 |
CN102371719B true CN102371719B (en) | 2013-08-07 |
Family
ID=45791211
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 201110250983 Expired - Fee Related CN102371719B (en) | 2011-08-29 | 2011-08-29 | Method for preparing copper/molybdenum/copper layered compound metallic material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102371719B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102941441B (en) * | 2012-11-02 | 2015-10-21 | 中南大学 | A kind of high bond strength high accuracy copper-molybdenum-copper laminated composite materials preparation method |
CN103406658B (en) * | 2013-06-17 | 2016-01-20 | 北京科技大学 | A kind of large scale tungsten copper flux of plasma parts preparation method |
CN104014921B (en) * | 2014-04-25 | 2016-04-27 | 长安大学 | A kind of method preparing copper molybdenum multilayer materials fast |
CN104741764A (en) * | 2015-03-10 | 2015-07-01 | 北京理工大学 | Method for preparing high-bonding-strength pure tungsten composite plate through preheated explosive welding |
CN104741765A (en) * | 2015-03-10 | 2015-07-01 | 北京理工大学 | Method for preparing high-bonding-strength pure-molybdenum composite board through hot explosive welding |
JP6455896B1 (en) * | 2017-11-18 | 2019-01-23 | Jfe精密株式会社 | Heat sink and manufacturing method thereof |
CN110712419A (en) * | 2019-09-24 | 2020-01-21 | 无锡乐普金属科技有限公司 | Preparation method of copper-molybdenum-copper alloy material |
CN113600999B (en) * | 2021-08-17 | 2022-09-30 | 合肥工业大学 | Explosive welding forming method for Mo/Cu composite board |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5942796A (en) * | 1997-11-17 | 1999-08-24 | Advanced Packaging Concepts, Inc. | Package structure for high-power surface-mounted electronic devices |
CN201037590Y (en) * | 2007-04-29 | 2008-03-19 | 南京宝泰特种材料有限公司 | Super austenitic stainless steel 904L composite board |
CN201380612Y (en) * | 2009-01-16 | 2010-01-13 | 安徽宝泰特种材料有限公司 | C-2000 alloy/steel explosive clad plate |
CN201448573U (en) * | 2009-06-10 | 2010-05-05 | 邓家爱 | Explosively clad plate formed by nickel-molybdenum alloy plate and steel plate |
CN101863151A (en) * | 2010-05-31 | 2010-10-20 | 闵小兵 | Method for preparing metal compound plate by continuously and accurately compounding comprehensive protective material on thin substrate and metal compound plate thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2717832B2 (en) * | 1989-01-12 | 1998-02-25 | 東京タングステン株式会社 | Composite metal material and its manufacturing method |
-
2011
- 2011-08-29 CN CN 201110250983 patent/CN102371719B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5942796A (en) * | 1997-11-17 | 1999-08-24 | Advanced Packaging Concepts, Inc. | Package structure for high-power surface-mounted electronic devices |
CN201037590Y (en) * | 2007-04-29 | 2008-03-19 | 南京宝泰特种材料有限公司 | Super austenitic stainless steel 904L composite board |
CN201380612Y (en) * | 2009-01-16 | 2010-01-13 | 安徽宝泰特种材料有限公司 | C-2000 alloy/steel explosive clad plate |
CN201448573U (en) * | 2009-06-10 | 2010-05-05 | 邓家爱 | Explosively clad plate formed by nickel-molybdenum alloy plate and steel plate |
CN101863151A (en) * | 2010-05-31 | 2010-10-20 | 闵小兵 | Method for preparing metal compound plate by continuously and accurately compounding comprehensive protective material on thin substrate and metal compound plate thereof |
Non-Patent Citations (3)
Title |
---|
JP平2-187285A 1990.07.23 |
Mo/Cu***复合棒界面组织特征;杨扬等;《中国钼业》;20070228;第31卷(第01期);第27-30页 * |
杨扬等.Mo/Cu***复合棒界面组织特征.《中国钼业》.2007,第31卷(第01期), |
Also Published As
Publication number | Publication date |
---|---|
CN102371719A (en) | 2012-03-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102371719B (en) | Method for preparing copper/molybdenum/copper layered compound metallic material | |
KR101754347B1 (en) | Warpage reduction in structures with electrical circuitry | |
CN105140144A (en) | Medium pressurized thermal annealing mixed bonding method | |
US20190002358A1 (en) | Copper-ceramic substrate, copper precursor for producing a copper-ceramic substrate and process for producing a copper-ceramic substrate | |
CN106271177B (en) | A kind of interconnection solder and its interconnection manufacturing process | |
JP2010093225A (en) | Substrate for power module with heat sink and method for manufacturing the same, power module with heat sink, and substrate for power module | |
CN108290380B (en) | Laminate and method for producing laminate | |
US20080230590A1 (en) | Method for fabricating dissimilar material jointed body | |
JP2011029323A (en) | Substrate for power module, power module, and method of manufacturing substrate for power module | |
JP2000040734A (en) | Semiconductor holding device, manufacture and use thereof | |
JP2006278558A (en) | Insulated heat transmission structure and substrate for use of power module | |
CN110169213B (en) | Method for manufacturing ceramic circuit board | |
CN110358508B (en) | Diamond-containing composite heat dissipation material and preparation method thereof | |
JP5521919B2 (en) | Manufacturing method of microchannel heat exchanger using magnetic refrigeration material | |
TW201841310A (en) | Manufacturing method of insulated circuit substrate with heat sink | |
CN101527287A (en) | Wire bond structure and producing method thereof | |
JP5046086B2 (en) | Ceramic substrate, ceramic circuit substrate and semiconductor module using the same | |
JP6546953B2 (en) | Sputtering target-backing plate assembly and method for manufacturing the same | |
CN105765749A (en) | Thermoelectric conversion module | |
CN105612614A (en) | Semiconductor device and semiconductor device manufacturing method | |
JP5861935B2 (en) | Inspection method for ceramic circuit boards | |
TWM481486U (en) | Flip-chip package device | |
JP4543275B2 (en) | Aluminum-ceramic bonding substrate and manufacturing method thereof | |
CN108713259A (en) | Thermo-electric conversion module | |
JP2010277809A (en) | Heater and device equipped with the same |
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: 20130807 Termination date: 20190829 |
|
CF01 | Termination of patent right due to non-payment of annual fee |