CN102828129B - Preparation method of Gd-Mn-based amorphous magnetic refrigeration material - Google Patents
Preparation method of Gd-Mn-based amorphous magnetic refrigeration material Download PDFInfo
- Publication number
- CN102828129B CN102828129B CN201210297377.9A CN201210297377A CN102828129B CN 102828129 B CN102828129 B CN 102828129B CN 201210297377 A CN201210297377 A CN 201210297377A CN 102828129 B CN102828129 B CN 102828129B
- Authority
- CN
- China
- Prior art keywords
- preparation
- amorphous magnetic
- magnetic
- based amorphous
- refrigeration 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.)
- Expired - Fee Related
Links
Landscapes
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to the field of magnetic materials and discloses a Gd-Mn-based amorphous magnetic refrigeration material and a preparation method thereof. The Gd-Mn-based amorphous magnetic refrigeration material has a chemical general formula of Gd65Mn35-xMx (x is greater than 0 and less than or equal to 10), wherein M represents Si or Ge. The preparation method comprises the following steps of 1, weighing pure elements according to a mass percentage of the elements shown in the chemical general formula and mixing, 2, repeatedly smelting the mixed elements to obtain a uniform alloy ingot, and 3, crushing the uniform alloy ingot into small blocks, and carrying out melt-spinning to obtain a stripe having the width of 1-2 millimeters and thickness of 30-50 micrometers, wherein the stripe is the Gd-Mn-based amorphous magnetic refrigeration material. The preparation method has simple processes, avoids long-term heat treatment, has a low cost and is suitable for industrial production. The Gd-Mn-based amorphous magnetic refrigeration material obtained by the preparation method can produce ferromagnetic-paramagnetic two-stage magnetic phase transition in magnetization, has a large refrigeration capacity and is suitable as a magnetic refrigeration material.
Description
Technical field
The present invention relates to a kind of amorphous magnetic material, particularly a kind of Gd-Mn base amorphous magnetic refrigerating material and preparation method thereof.
Background technology
Along with the enhancing of people's environmental consciousness, the increasing the weight of of global energy crisis, traditional gas compression Refrigeration Technique is subject to increasing dispute and challenge.Even constantly remove from office under news in technology, its refrigerating efficiency still only has the 5-10% of the contrary circulation of Carnot Engine, and energy consumption is very serious.Simultaneously traditional gas refrigeration technology adopts chemical liquid refrigeration working medium (as freonll-11), easily discharges the chemical substance damaging the ozone layer in refrigerator working process, causes global greenhouse effect aggravation.Current, emerging Refrigeration Technique mainly contains thermoelectric refrigeration and magnetic Refrigeration Technique, and thermoelectric refrigeration is that peltier effect (Peltier effect) based on material is realized, be mainly used in space aerospace or military communication aspect, be difficult to realize its commercial value.Magnetic Refrigeration Technique is that the magnetothermal effect (Magnetocaloric effect) based on material realizes, this Refrigeration Technique can be saved the energy that 20-30% gas refrigeration technology consumes, and magnetic refrigerator uses solid coolant working medium, can effectively alleviate the destruction problem of refrigeration agent to ozonosphere, magnetic refrigerator does not need compressor to do work to gas, the advantage such as have that energy consumption is low, pollution-free, low noise, volume are little, easy care, life-span are long.As the Refrigeration Technique of environmental protection, magnetic refrigeration has received global concern.Wherein, magnetic refrigerating working material is one of technology of magnetic refrigeration most critical, requires magnetism of material transition temperature point near operating temperature range, magnetothermal effect large (being that isothermal magnetic entropy becomes greatly), and relative low price, environment friendly and pollution-free etc.
At present, the magnetic refrigerating material of studying is mainly divided into one-level magnetic phase change material and secondary magnetic phase change material.The Gd of U.S.'s Ames Lab discovery in 1997
5si
2ge
2the La (Fe, Si) that (5:4 system), calendar year 2001 Chinese Academy of Sciences's CAS Institute of Physics Hu Fengxia etc. find
13the Mn-Fe-P-As compound of (1:13 system), Tegus in 2002 report and Heusler alloy Ni-Mn-X (X=Ga afterwards, Sn, In, Sb) all near magnetic transition temperature, there is first-order phase transition and obtain huge magnetothermal effect, but becoming, the magnetic entropy of the type magnetic refrigerating material undergos mutation near transition temperature, transition temperature region is narrower, is difficult to meet Ericsson magnetic refrigeration cycle magnetic entropy is become and within the scope of wide warm area, keeps substantially invariable requirement; And that the magnetic entropy of second-order phase transition magnetic refrigerating material becomes near temperature span its magnetic transition temperature is larger, magnetic entropy change is milder, and refrigerating duty is large.Pure Gd is typical second-order phase transition material, but the chemical property of Gd is active, and oxidizable, solidity to corrosion is poor, and physical strength is lower, expensive, and commercialization still exists some problems.Non-crystalline material is also a kind of typical secondary magnetic phase change material, and non-crystalline material has high thermal conductivity and specific conductivity and good solidity to corrosion, is expected to become the very competitive magnetic refrigerating working material of one.
Summary of the invention
Object of the present invention is overcoming the defect of prior art, a kind of Stability Analysis of Structures, environmental protection is provided and has the Gd-Mn base amorphous magnetic refrigerating material of larger refrigerating duty.
Another object of the present invention has been to provide the preparation method of above-mentioned amorphous magnetic refrigerating material.
Object of the present invention is achieved through the following technical solutions:
A kind of Gd-Mn base amorphous magnetic refrigerating material, its chemical general formula is: Gd
65mn
35-xm
x(0<x≤10), in formula, M is Si or Ge.
Preferably, described x=5,10.
The preparation method of described Gd-Mn base amorphous magnetic refrigerating material, comprises the steps:
(1) taking pure element according to the mass percent of each element in above-mentioned general formula mixes;
(2) above-mentioned complex element is carried out to melt back, obtain uniform alloy cast ingot;
(3) ingot casting obtained above is broken into fritter, utilization is got rid of band method and is obtained the wide 1-2mm of being, thickness is the band of 30 ~ 50 μ m, is amorphous magnetic refrigerating material.
Preferably, the melting condition described in step (2) is vacuum arc melting, is evacuated to 4.0 × 10
-3pa, adopt high-purity Ar clean burner hearth, be filled with lower than 1 atmospheric high-purity argon gas as protection gas, in fusion process using titanium sponge as absorb carrier.
Preferably, described in step (3), get rid of SNNP: adopt induction melting, be evacuated to 8.0 × 10
-4pa, adopt high-purity argon clean burner hearth, and with argon gas as protect gas, the tangential linear velocity of copper roller is 45 ~ 50m/s, gets rid of the poor 0.08 ~ 0.09MPa of being of silica tube external and internal pressure in band process.
Preferably, described in step (3), the tangential linear velocity of copper roller is 50m/s, gets rid of the poor 0.08MPa of being of silica tube external and internal pressure in band process.
The present invention compared with prior art tool has the following advantages and effect:
(1) preparation technology of the present invention is comparatively simple, need not any thermal treatment, reduce cost, and be applicable to suitability for industrialized production.
(2) prepared Gd
65mn
35-xsi
x(0<x≤10) and Gd
65mn
35-xge
x(0<x≤10) non-crystaline amorphous metal is in the time of x=5 and 10, respectively 221,218,212, there is the typical ferromagnetic second-order phase transition to paramagnetic near 229K, under Δ H=50kOe the action of a magnetic field, its corresponding magnetic entropy becomes value and is respectively 4.56,4.68,4.14 and 4.50Jkg
-1k
-1, and its refrigeration value is respectively 625,660,625 and 615J/kg, and large refrigerating duty explanation magnetic transformation temperature, across larger, is suitable as the magnetic refrigerating working material of 150 ~ 250K temperature range very much.
Brief description of the drawings
Fig. 1 is Gd
65mn
35-xsi
x(x=5,10) and Gd
65mn
35-xge
x(x=5,10) alloy strip X-ray diffractogram at room temperature.
Fig. 2 (a), Fig. 2 (b) are respectively Gd
65mn
35-xsi
x(x=5,10) and Gd
65mn
35-xge
xthe DSC graphic representation of (x=5,10) alloy strip between 303K to 973K.
Fig. 3 is Gd
65mn
35-xsi
x(x=5,10) and Gd
65mn
35-xge
x(x=5, the 10) specific magnetising moment of alloy strip and the relation curve of temperature.
Fig. 4 (a), Fig. 4 (b) are respectively Gd
65mn
25si
10with Gd
65mn
25ge
10the Arrott graphic representation of alloy strip.
Fig. 5 is Gd
65mn
35-xsi
x(x=5,10) and Gd
65mn
35-xge
xthe isothermal magnetic entropy of (x=5,10) alloy strip becomes the relation curve with temperature.
Embodiment
Below in conjunction with embodiment, the present invention is done to further detailed description, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of preparation method of Gd-Mn base amorphous magnetic refrigerating material is as follows:
Step 1: by pure element Gd, Mn and Si according to Gd
65mn
35-xsi
xin (x=5,10), the mass percent of each element samples mixing, and sample name gross weight is 10g;
Step 2: the above-mentioned raw material preparing is put into vacuum arc fumace, adopt sponge Ti to absorb atmosphere crucible, take out respectively rough vacuum and high vacuum to 4.0 × 10
-3pa, adopts high-purity argon gas to clean burner hearth, and the high-purity argon gas of be filled with approximately-0.02MPa is as protection gas, and melt back 5 times, obtains the uniform button shape of composition ingot casting after cooling;
Step 3: by the ingot casting fragmentation after melting, put into silica tube, adopt induction melting, be evacuated to 8.0 × 10
-4pa, adopts high-purity argon to clean burner hearth, and with argon gas as protection gas, the tangential linear velocity of copper roller is 45m/s, getting rid of in band process silica tube external and internal pressure poor is 0.08MPa, obtain the wide 1mm of being, thick be the band of 30 ~ 50 μ m.
The band obtaining through above-mentioned three steps proves through X-ray diffraction analysis, and band does not present the diffraction peak corresponding with crystal, is complete non-crystal structure, as shown in Figure 1.Fig. 2 (a) is Gd
65mn
35-xsi
xthe DSC curve of (x=5,10) sample, once starts crystallization temperature T by the known sample of curve
x1be respectively 615 and 590K, far above room temperature (300K), illustrate that this amorphous sample can stable existence in room temperature.
Fig. 3 measures the specific magnetising moment of band and the relation curve of temperature by physical property system ensemble (PPMS), the magnetic transition temperature of material corresponding to the specific magnetising moment to the corresponding temperature of temperature derivative minimum value.Gd
65mn
35-xsi
xthe transition temperature of (x=5,10) amorphous ribbon sample is respectively 221K (x=5), 218K (x=10).
According to Landau theory, can calculate the Arrott curve of sample at each temperature by the isothermal magnetization curve of sample, when Arrott slope of a curve is for just, phase transition property is second-order phase transition; Otherwise phase transition property is first-order phase transition.Fig. 4 (a) is Gd
65mn
25si
10the Arrott curve of amorphous ribbon, in figure slope of a curve be on the occasion of, be secondary magnetic phase transition therefore this sample occurs.According to Maxwell relational expression, the isothermal magnetic entropy that utilizes near the isothermal magnetization opisometer of differing temps sample Curie temperature to calculate non-crystaline amorphous metal becomes, as shown in Fig. 5 (a).Gd
65mn
35-xsi
xnon-crystaline amorphous metal is worked as x=5, and 10 o'clock magnetic entropies under Δ H=20kOe and 50kOe external magnetic field become and are respectively 2.28 and 4.56Jkg
-1k
-1, 2.33 and 4.68Jkg
-1k
-1.
In order better to evaluate the refrigerating efficiency of magnetic refrigeration working substance, refrigerating duty RC is used as an evaluating, according to calculation formula
wherein T
1, T
2represent that magnetic entropy becomes the low-temperature end corresponding with halfwidth in temperature curve and the temperature value of temperature end.Gd
65mn
35-xsi
xnon-crystaline amorphous metal is worked as x=5, and 10 o'clock refrigerating duty RC under Δ H=50kOe external magnetic field are about respectively 625 and 660J/kg.
By embodiment 1 and crystalline material Gd
5si
2ge
2, LaFe
1.14si
1.6and Ni
45co
5mn
36.7in1
3.3refrigerating duty contrast, as shown in table 1, the refrigerating duty of this kind of amorphous alloy, much larger than above-mentioned crystalline material, illustrates Gd
65mn
35-xsi
xthe temperature of (x=5,10) non-crystalline material, across larger, is more conducive to be applicable to Sven-Gan Eriksson magnetic refrigeration cycle.
Embodiment 2
A kind of Gd-Mn base amorphous magnetic refrigerating material, its preparation method is as follows:
Step 1: by pure element Gd, Mn and Ge according to Gd
65mn
35-xge
xin (x=5,10), the mass percent of each element samples mixing, and sample name gross weight is 10g;
Step 2: the above-mentioned raw material preparing is put into vacuum arc fumace, adopt sponge Ti to absorb atmosphere crucible, take out respectively rough vacuum and high vacuum to 4.0 × 10
-3pa, adopts high-purity argon to clean burner hearth, and the high-purity argon gas of be filled with approximately-0.02MPa is as protection gas, and melt back 5 times, obtains the uniform button shape of composition ingot casting after cooling;
Step 3: by the ingot casting fragmentation after melting, put into silica tube, adopt induction melting, be evacuated to 8.0 × 10
-4pa, adopts high-purity argon to clean burner hearth, and with argon gas as protection gas, the tangential linear velocity of copper roller is 50m/s, getting rid of in band process silica tube external and internal pressure poor is 0.08MPa, obtain the wide 1mm of being, thick be the band of 30 ~ 50 μ m.
The band obtaining through above-mentioned three steps proves through X-ray diffraction analysis, and band does not present the diffraction peak corresponding with crystal, is complete non-crystal structure, as shown in Figure 1.Fig. 2 (b) is Gd
65mn
35-xge
xthe DSC curve of (x=5,10) sample, once starts crystallization temperature T by the known sample of curve
x1be respectively 685 and 645K, also illustrate that this amorphous sample can stable existence in room temperature.
Fig. 3 measures the specific magnetising moment of band and the relation curve of temperature by physical property system ensemble (PPMS), the magnetic transition temperature of material corresponding to the specific magnetising moment to the corresponding temperature of temperature derivative minimum value.Gd
65mn
35-xge
xthe transition temperature of (x=5,10) amorphous ribbon sample is respectively 212K (x=5), 229K (x=10).
According to Landau theory, can calculate the Arrott curve of sample at each temperature by the isothermal magnetization curve of sample, when Arrott slope of a curve is for just, phase transition property is second-order phase transition; Otherwise phase transition property is first-order phase transition.Fig. 4 (b) is Gd
65mn
25ge
10the Arrott curve of amorphous ribbon, in figure slope of a curve be on the occasion of, be secondary magnetic phase transition therefore such sample occurs.According to Maxwell relational expression, the isothermal magnetic entropy that utilizes near the isothermal magnetization opisometer of differing temps sample Curie temperature to calculate non-crystaline amorphous metal becomes, as shown in Figure 5, and Gd
65mn
35-xge
xnon-crystaline amorphous metal is worked as x=5, and 10 o'clock magnetic entropies under Δ H=20kOe and 50kOe external magnetic field become and are respectively 2.00 and 4.14Jkg
-1k
-1, 2.16 and 4.50Jkg
-1k
-1.Gd
65mn
35-xge
xnon-crystaline amorphous metal is worked as x=5, and 10 o'clock refrigerating duty RC under 50kOe are about respectively 625 and 615J/kg.
By example 2 and crystalline material Gd
5si
2ge
2, LaFe
11.4si
1.6contrast with the refrigerating duty of NiMnSn, as shown in table 1.Can find out that the temperature of such non-crystalline material is across larger, more be conducive to be applicable to Sven-Gan Eriksson magnetic refrigeration cycle.
Table 1 magnetic parameter of being correlated with
Note: a-represents amorphous; C-represents crystal.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other do not deviate from the change done under spirit of the present invention and principle, modification, substitute, combination, simplify; all regard as equivalent substitute mode, within being included in protection scope of the present invention.
Claims (2)
1. a preparation method for Gd-Mn base amorphous magnetic refrigerating material, is characterized in that, comprises the steps:
(1) according to chemical general formula: Gd
65mn
35-xm
xin (5≤x≤10), the mass percent of each element takes pure element and mixes, and in formula, M is Si;
(2) above-mentioned complex element is carried out to melt back, obtain uniform alloy cast ingot;
(3) ingot casting obtained above is broken into fritter, utilizes and get rid of band method and obtain the wide 1～2mm of being, thickness is the band of 30～50 μ m, the described SNNP that gets rid of: adopt induction melting, be evacuated to 8.0 × 10
-4pa, adopt high-purity argon clean burner hearth, and with argon gas as protect gas, the tangential linear velocity of copper roller is 45～50m/s, gets rid of the poor 0.08～0.09MPa of being of silica tube external and internal pressure in band process, is amorphous magnetic refrigerating material;
Melting condition described in step (2) is vacuum arc melting, is evacuated to 4.0 × 10
-3pa, adopt high-purity Ar clean burner hearth, be filled with lower than 1 atmospheric high-purity argon gas as protection gas, in fusion process using titanium sponge as absorb carrier.
2. the preparation method of Gd-Mn base amorphous magnetic refrigerating material according to claim 1, described in step (3), the tangential linear velocity of copper roller is 50m/s, getting rid of in band process silica tube external and internal pressure poor is 0.08MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210297377.9A CN102828129B (en) | 2012-08-20 | 2012-08-20 | Preparation method of Gd-Mn-based amorphous magnetic refrigeration material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210297377.9A CN102828129B (en) | 2012-08-20 | 2012-08-20 | Preparation method of Gd-Mn-based amorphous magnetic refrigeration material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102828129A CN102828129A (en) | 2012-12-19 |
| CN102828129B true CN102828129B (en) | 2014-12-03 |
Family
ID=47331434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210297377.9A Expired - Fee Related CN102828129B (en) | 2012-08-20 | 2012-08-20 | Preparation method of Gd-Mn-based amorphous magnetic refrigeration material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102828129B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106601399B (en) * | 2016-12-13 | 2018-05-15 | 华南理工大学 | A kind of compound magnetic refrigerating material and preparation method thereof |
| WO2019164982A1 (en) * | 2018-02-22 | 2019-08-29 | General Engineering & Research, L.L.C. | Magnetocaloric alloys useful for magnetic refrigeration applications |
| CN115976389B (en) * | 2022-11-25 | 2024-05-31 | 中国科学院宁波材料技术与工程研究所 | Magnetic refrigeration Gd-based material with platform type magnetic entropy change curve and preparation and application thereof |
| CN117840422B (en) * | 2024-03-08 | 2024-06-14 | 朗峰新材料启东有限公司 | Manganese-based amorphous nanocrystalline composite powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328566A (en) * | 2008-07-30 | 2008-12-24 | 电子科技大学 | Block rare earth gadolinium-based composite amorphous material and preparation thereof |
| CN102242301A (en) * | 2011-07-05 | 2011-11-16 | 华南理工大学 | Gd-base room-temperature magnetic cold material and preparation method thereof |
-
2012
- 2012-08-20 CN CN201210297377.9A patent/CN102828129B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328566A (en) * | 2008-07-30 | 2008-12-24 | 电子科技大学 | Block rare earth gadolinium-based composite amorphous material and preparation thereof |
| CN102242301A (en) * | 2011-07-05 | 2011-11-16 | 华南理工大学 | Gd-base room-temperature magnetic cold material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Critical behavior and magnetocaloric effect of Gd65Mn35-xGex(x=0,5,and 10) melt-spun ribbons;X.C.Zhong et al.;《JOURNAL OF APPLIED PHYSICS》;20120802;第112卷(第3期);第1页右栏第2段，第2页左栏第2段 * |
| X.C.Zhong et al..Critical behavior and magnetocaloric effect of Gd65Mn35-xGex(x=0,5,and 10) melt-spun ribbons.《JOURNAL OF APPLIED PHYSICS》.2012,第112卷(第3期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102828129A (en) | 2012-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Large refrigerant capacity induced by table-like magnetocaloric effect in amorphous Er0. 2Gd0. 2Ho0. 2Co0. 2Cu0. 2 ribbons | |
| Barua et al. | Anisotropic magnetocaloric response in AlFe2B2 | |
| Brück et al. | Magnetocaloric effects in MnFeP1− xAsx-based compounds | |
| CN101550521B (en) | Rare-earth-based bulk amorphous alloy with magnetothermal effect and composite material thereof | |
| TW201001895A (en) | Thermomagnetic generator | |
| CN102828129B (en) | Preparation method of Gd-Mn-based amorphous magnetic refrigeration material | |
| CN104946954B (en) | A kind of MnCoGe base magnetic materials with huge piezocaloric effect and its production and use | |
| CN101413093A (en) | Block gadolinium-based composite amorphous magnetic cooling material and preparation thereof | |
| CN102383018B (en) | Preparation method of rare earth-chrome-silicone-based magnetic refrigerating material | |
| CN106554006A (en) | A kind of material with carbon element, preparation method and applications | |
| Saidi et al. | Review of the influence of copper and chromium substitution on crystal structure, magnetic properties and magnetocaloric effect of GdFe2− x (Cu, Cr) x (x= 0, 0.1, 0.15 and 0.2) intermetallic compounds | |
| CN101923933B (en) | Hydrogenated NiMn-based alloy magnetic refrigeration material and preparation method and use thereof | |
| CN106191616B (en) | A kind of magnetic phase transition alloy | |
| Cheng et al. | Refrigeration effect of La (FeCoSi) 13B0. 25 compounds and gadolinium metal in reciprocating magnetic refrigerator | |
| CN106702245B (en) | A kind of Gd-Co based amorphous nano magnetic refrigerating material and preparation method thereof | |
| Huang et al. | Preparation, crystal structure and magnetocaloric properties of Tb 5 (Si x Ge 4− x) | |
| Liang et al. | Thermal stability and magnetocaloric properties of GdDyAlCo bulk metallic glasses | |
| CN106935348A (en) | A kind of Gd basal cells temperature magnetic refrigerating material and preparation method thereof | |
| CN102703038B (en) | Gd-based magnetic refrigeration material and preparation method thereof | |
| Tian et al. | Structure, magnetic and magnetocaloric properties of polycrystalline Er3AlC compound | |
| Wang et al. | Giant enhancement of magnetocaloric effect in metallic glass matrix composite | |
| Balli et al. | Effect of Ni substitution on the magnetic and magnetocaloric properties of the Dy (Co1− xNix) 2 Laves phase | |
| CN107881394A (en) | A kind of Ni Co Mn In Ge magnetic refrigeration alloy material and preparation method | |
| CN102978422B (en) | Preparation method and application of rare earth-nickel-silicon material with large magnetothermal effect | |
| CN1312706C (en) | Rare earth iron-base room-temp mangnetic refrigerant material and preparation 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: 20141203 Termination date: 20200820 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |