CN103332744A - Method for preparing h-MoO3 nano rod in microwave-ultraviolet mode - Google Patents
Method for preparing h-MoO3 nano rod in microwave-ultraviolet mode Download PDFInfo
- Publication number
- CN103332744A CN103332744A CN2013102447778A CN201310244777A CN103332744A CN 103332744 A CN103332744 A CN 103332744A CN 2013102447778 A CN2013102447778 A CN 2013102447778A CN 201310244777 A CN201310244777 A CN 201310244777A CN 103332744 A CN103332744 A CN 103332744A
- Authority
- CN
- China
- Prior art keywords
- microwave
- solution
- ultraviolet
- moo
- nanometer rod
- 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
Images
Abstract
The invention discloses a method for preparing an h-MoO3 nano rod in a microwave-ultraviolet mode. The method comprises the following steps of: adding ammonium molybdate into deionized water to obtain a solution A, adjusting the pH value of the solution A to be 0.5-2.0 so as to obtain a solution B, pouring the solution B into a four-neck round-bottom flask and putting into a microwave-ultraviolet-ultrasonic integral synthesis extraction reaction instrument, naturally cooling to be the room temperature after the reaction is accomplished, taking out a product, washing and putting into an electro-thermal vacuum drying tank to be dried so as to obtain the h-MoO3 nano rod. By utilizing the method, the synthesis technique range of h-MoO3 nano crystal is expanded, the process for preparing the h-MoO3 nano rod is simple, raw materials are easy to obtain, the yield is high, the reaction period is short, the cost is low, the h-MoO3 nano rod prepared by using the method is complete in growth and high in purity and has high oriented growth characteristics, and h-MoO3 nano rods can be synthesized in a large scale.
Description
Technical field
The present invention relates to a kind of preparation MoO
3The method of nanometer rod, particularly a kind of employing microwave-ultraviolet prepares h-MoO
3The method of nanometer rod.
Technical background
MoO
3As a kind of important function inorganic materials, be the core material of devices such as electrochromism, photochromic, gas-discoloration, gas sensing, intelligence camouflage, have great application prospect in fields such as energy-conservation, the information demonstration of building and automobile and storage, environmental monitoring, foodstuffs industry, military affairs.MoO
3Three kinds of common crystalline structures are arranged: thermodynamically stable quadrature phase α-MoO
3, the monocline phase β-MoO of thermodynamics metastable structure
3With six sides h-MoO mutually
3The h-MoO of six side's phases
3Nanocrystalline because have renewal, more superior physical and chemical activity more and more is subjected to investigator's extensive concern.Seek h-MoO
3Nanocrystalline simply, synthetic method effectively and rapidly, explore h-MoO
3Nanocrystalline at theoretical aspect optics, electricity and the catalysis with use and all will be of practical significance more.At present about h-MoO
3Nanocrystalline method all is some traditional preparation methods, as sonochemistry method, hydrothermal method etc.[S.R.Dhage, M.S.Hassan, O.Bong Yang, Low temperature fabrication of hexagon shaped h-MoO such as S.R.Dhage
3Nanorods and its phase transformation [ J ] .Materials Chemistry and Physics, 2009,114:511-514] ammonium molybdate, urea, sodium lauryl sulphate have been synthesized six side's phase h-MoO with the method for ultrasound probe down at 70 ℃
3Nanometer rod; [Zhuangzhi Wu such as the Wu Zhuanzhi of Central South University, Dezhi Wang, Xun Liang, Aokui Sun, Ultrasonic-assisted preparation of metastable hexagonal MoO3nanorods and their transformation to microbelts[J], Ultrasonics Sonochemistry, 2011,18:288-292] be that raw material has successfully prepared h-MoO with the sonochemistry method with ammonium dimolybdate and hydrochloric acid
3Nanometer rod.[Lei Zheng, Yang Xu, Dong Jin, and Yi Xie, the Novel Metastable Hexagonal MoO such as Lei Zheng in Anhui nano material and nanochemistry laboratory
3Nanobelts:Synthesis, Photochromic, and Electrochromic Properties[J], Chem.Mater, 2009,21:5681-5690] and with Mo powder, H
2O
2And NaNO
3For raw material adopts hydrothermal method insulation 12h to synthesize h-MoO down at 150 ℃
3Nano belt; [A.Chithambararaj, A.Chandra Bose, Hydrothermal synthesis of hexagonal and orthorhombic MoO such as A.Chithambararaj
3Nanoparticles[J] .Journal of Alloys and Compounds, 2011,509:8105-8110] under 90 ℃, also adopt hydrothermal method to synthesize six sides h-MoO mutually in ammonium molybdate and nitric acid
3Nano particle.Because the synthetic h-MoO of hydrothermal method
3Nanocrystallinely there are shortcomings such as temperature of reaction is higher relatively, long reaction time, and the synthetic h-MoO of sonochemistry method
3Nanocrystalline existence reaction is not easy control, shortcoming such as side reaction generation is arranged, so seek a kind of low temperature, easily control, synthetic h-MoO fast
3Nanocrystalline method has great importance.
Summary of the invention
The object of the present invention is to provide a kind of employing microwave-ultraviolet to prepare h-MoO
3The method of nanometer rod, this method equipment is simple, control, and suitable scale operation easily; Raw materials used simple, can synthesize h-MoO cheaply
3Nanometer rod; The h-MoO that makes by preparation method of the present invention
3Nanometer rod purity height, the crystallization homogeneity is higher, and crystal has tangible oriented growth trend.
For achieving the above object, the preparation method that the present invention adopts is as follows:
1) with analytically pure (NH
4)
6Mo
7O
244H
2It is the solution A of 0.005~0.05mol/L that O joins the concentration that deionized water for stirring makes ammonium molybdate;
2) with the solution A stirring and dissolving evenly the pH value of back regulator solution A be 0.5~2.0 must solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round bottom flask that are equipped with are gone in the synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 40~80 ℃ of temperature of reaction, time 60~120min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity, the taking-up product washs the electric vacunm drying case inner drying that is placed on 50~70 ℃ and namely obtains h-MoO
3Nanometer rod.
Described step 2) HNO of employing 3~6mol/L
3The pH value of solution regulator solution A is 0.5~2.0.
The synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity of described step 3) adopts the synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity of UWave-1000 type.
Described step 5) washing employing deionized water and dehydrated alcohol repeated washing 3~7 times.
Useful effect: the present invention has enlarged h-MoO
3Nanocrystalline synthetic technology scope; Preparation h-MoO
3Nanometer rod technology is simple, and raw material is easy to get, and productive rate is higher, and reaction time is short, and cost is low; H-MoO by the inventive method gained
3Nanometer rod is grown complete, and purity is higher, has higher oriented growth characteristic; The h-MoO that can synthesize on a large scale
3Nanometer rod.
Description of drawings
Fig. 1 is the h-MoO of the inventive method preparation
3Nanocrystalline XRD figure spectrum.
Fig. 2 is the h-MoO of the inventive method preparation
3The SEM photo of nanometer rod.
Embodiment
Embodiment 1:
1) with analytical pure ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) joining the concentration that deionized water for stirring makes ammonium molybdate is the solution A of 0.005mol/L;
2) with the solution A stirring and dissolving evenly after, adopt the HNO of 3mol/L
3The pH value of solution regulator solution A be 1.0 solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round-bottomed flasks that are equipped with are put into the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 60 ℃ of temperature of reaction, time 100min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, take out product, the electric vacunm drying case inner drying that adopts deionized water and dehydrated alcohol repeated washing to be placed on 60 ℃ for 3~7 times successively namely obtains h-MoO
3Nanometer rod.
Embodiment 2:
1) with analytical pure ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) joining the concentration that deionized water for stirring makes ammonium molybdate is the solution A of 0.01mol/L;
2) with the solution A stirring and dissolving evenly after, adopt the HNO of 4mol/L
3The pH value of solution regulator solution A be 1.5 solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round-bottomed flasks that are equipped with are put into the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 70 ℃ of temperature of reaction, time 90min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, take out product, the electric vacunm drying case inner drying that adopts deionized water and dehydrated alcohol repeated washing to be placed on 70 ℃ for 3~7 times successively namely obtains h-MoO
3Nanometer rod.
Embodiment 3:
1) with analytical pure ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) joining the concentration that deionized water for stirring makes ammonium molybdate is the solution A of 0.008mol/L;
2) with the solution A stirring and dissolving evenly after, adopt the HNO of 5mol/L
3The pH value of solution regulator solution A be 0.8 solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round-bottomed flasks that are equipped with are put into the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 50 ℃ of temperature of reaction, time 120min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, take out product, the electric vacunm drying case inner drying that adopts deionized water and dehydrated alcohol repeated washing to be placed on 50 ℃ for 3~7 times successively namely obtains h-MoO
3Nanometer rod.
Embodiment 4:
1) with analytical pure ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) joining the concentration that deionized water for stirring makes ammonium molybdate is the solution A of 0.02mol/L;
2) with the solution A stirring and dissolving evenly after, adopt the HNO of 6mol/L
3The pH value of solution regulator solution A be 1.5 solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round-bottomed flasks that are equipped with are put into the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 60 ℃ of temperature of reaction, time 100min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, take out product, the electric vacunm drying case inner drying that adopts deionized water and dehydrated alcohol repeated washing to be placed on 70 ℃ for 3~7 times successively namely obtains h-MoO
3Nanometer rod.
Embodiment 5:
1) with analytical pure ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) joining the concentration that deionized water for stirring makes ammonium molybdate is the solution A of 0.03mol/L;
2) with the solution A stirring and dissolving evenly after, adopt the HNO of 4mol/L
3The pH value of solution regulator solution A be 0.5 solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round-bottomed flasks that are equipped with are put into the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 40 ℃ of temperature of reaction, time 110min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, take out product, the electric vacunm drying case inner drying that adopts deionized water and dehydrated alcohol repeated washing to be placed on 55 ℃ for 3~7 times successively namely obtains h-MoO
3Nanometer rod.
Embodiment 6:
1) with analytical pure ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) joining the concentration that deionized water for stirring makes ammonium molybdate is the solution A of 0.05mol/L;
2) with the solution A stirring and dissolving evenly after, adopt the HNO of 6mol/L
3The pH value of solution regulator solution A be 2.0 solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round-bottomed flasks that are equipped with are put into the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 80 ℃ of temperature of reaction, time 60min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the UWave-1000 type microwave ultraviolet excess sound wave trinity, take out product, the electric vacunm drying case inner drying that adopts deionized water and dehydrated alcohol repeated washing to be placed on 65 ℃ for 3~7 times successively namely obtains h-MoO
3Nanometer rod.
As can be seen from Figure 1, prepared h-MoO
3The nanometer rod good crystallinity, purity is higher, and significantly oriented growth characteristic is arranged.The nanometer rod of present method preparation physically well develops as can be seen from Figure 2.
Claims (4)
1. one kind is adopted microwave-ultraviolet to prepare h-MoO
3The method of nanometer rod is characterized in that may further comprise the steps:
1) with analytically pure (NH
4)
6Mo
7O
244H
2It is the solution A of 0.005~0.05mol/L that O joins the concentration that deionized water for stirring makes ammonium molybdate;
2) with the solution A stirring and dissolving evenly the pH value of back regulator solution A be 0.5~2.0 must solution B;
3) solution B is poured in the four neck round-bottomed flasks, the four neck round bottom flask that are equipped with are gone in the synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity, and fix, adopt direct temperature measurement mode thermometric (platinum resistor temperature measuring);
4) adopt microwave-ultraviolet synthesis model, the power of ultraviolet lamp is 300W, ultraviolet lamp centre wavelength is 365nm, select temperature-time service pattern, set 40~80 ℃ of temperature of reaction, time 60~120min, microwave heating time is made as 10min, the output rating of insulating process microwave is 24W, and reaction naturally cools to room temperature after finishing;
5) open the synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity, the taking-up product washs the electric vacunm drying case inner drying that is placed on 50~70 ℃ and namely obtains h-MoO
3Nanometer rod.
2. employing microwave-ultraviolet according to claim 1 prepares h-MoO
3The method of nanometer rod is characterized in that: the HNO that described step 2) adopts 3~6mol/L
3The pH value of solution regulator solution A is 0.5~2.0.
3. employing microwave-ultraviolet according to claim 1 prepares h-MoO
3The method of nanometer rod is characterized in that: the synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity of described step 3) adopts the synthetic extractive reaction instrument of the microwave ultraviolet excess sound wave trinity of UWave-1000 type.
4. employing microwave-ultraviolet according to claim 1 prepares h-MoO
3The method of nanometer rod is characterized in that: described step 5) washing employing deionized water and dehydrated alcohol repeated washing 3~7 times.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310244777.8A CN103332744B (en) | 2013-06-19 | 2013-06-19 | A kind of microwave-ultraviolet that adopts prepares h-MoO 3the method of nanometer rod |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310244777.8A CN103332744B (en) | 2013-06-19 | 2013-06-19 | A kind of microwave-ultraviolet that adopts prepares h-MoO 3the method of nanometer rod |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103332744A true CN103332744A (en) | 2013-10-02 |
CN103332744B CN103332744B (en) | 2015-08-19 |
Family
ID=49240973
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310244777.8A Active CN103332744B (en) | 2013-06-19 | 2013-06-19 | A kind of microwave-ultraviolet that adopts prepares h-MoO 3the method of nanometer rod |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103332744B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103771516A (en) * | 2014-01-24 | 2014-05-07 | 天津理工大学 | Preparation method of hexagonal-phase molybdenum trioxide microrod |
CN109052475A (en) * | 2018-09-27 | 2018-12-21 | 济南大学 | A kind of rodlike MoO of area load particle3/ZnMoO4The synthetic method of structure |
CN110085860A (en) * | 2019-04-26 | 2019-08-02 | 陕西科技大学 | A kind of preparation method of phosphorized copper nanotube |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103086435A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院兰州化学物理研究所 | Preparation method of molybdenum trioxide nanorod |
-
2013
- 2013-06-19 CN CN201310244777.8A patent/CN103332744B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103086435A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院兰州化学物理研究所 | Preparation method of molybdenum trioxide nanorod |
Non-Patent Citations (3)
Title |
---|
MASAHIKO OSAKA ET AL.: "Morphology-controlled synthesis of Mo compounds from a nitric acid solution by the microwave heating and/or Zr-addition", 《JOURNAL OF NUCLEAR MATERIALS》 * |
刘志等: "室温离子液体对花球状α-氧化钼微波加热合成产物结构的影响", 《材料导报》 * |
赵文彦等: "《辐射加工技术及其应用》", 31 March 2003, 兵器工业出版社 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103771516A (en) * | 2014-01-24 | 2014-05-07 | 天津理工大学 | Preparation method of hexagonal-phase molybdenum trioxide microrod |
CN109052475A (en) * | 2018-09-27 | 2018-12-21 | 济南大学 | A kind of rodlike MoO of area load particle3/ZnMoO4The synthetic method of structure |
CN110085860A (en) * | 2019-04-26 | 2019-08-02 | 陕西科技大学 | A kind of preparation method of phosphorized copper nanotube |
CN110085860B (en) * | 2019-04-26 | 2020-09-22 | 陕西科技大学 | Preparation method of copper phosphide nanotube |
Also Published As
Publication number | Publication date |
---|---|
CN103332744B (en) | 2015-08-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hu et al. | Ti3+ self-doped mesoporous black TiO2/SiO2 nanocomposite as remarkable visible light photocatalyst | |
CN104477972B (en) | A kind of ion liquid microemulsion thermal synthesis ZnIn 2s 4type photocatalyst and preparation method | |
CN102502791B (en) | Method for preparing flower-cluster-shaped tin sulfide (SnS) nanometer particles by microwave hydrothermal method | |
Li et al. | Hydrothermal synthesis of mesoporous InVO4 hierarchical microspheres and their photoluminescence properties | |
CN103240074A (en) | Bismuth vanadate light catalyst for exposing high-activity crystal face and preparation method for bismuth vanadate light catalyst | |
CN103332744B (en) | A kind of microwave-ultraviolet that adopts prepares h-MoO 3the method of nanometer rod | |
CN103922384A (en) | Method for preparing cubic phase Sm2O3 nano crystal with combination of uniform precipitation-thermal treatment | |
CN102936044B (en) | Method for synthesizing hexagonal rod-shaped MoO3 microcrystalline through hydrothermal method | |
CN103332747B (en) | A kind of low temperature synthesis h-MoO 3the method of micron bar | |
CN104925863A (en) | Preparation method of monoclinic structure vanadium dioxide powder | |
CN102951686A (en) | Preparation method for granular manganese tungstate nanocrystals | |
CN103818959A (en) | Low-temperature hydrothermal preparation method of molybdenum trioxide nanorod material | |
CN103332742A (en) | Method for preparing alpha-MoO3 nanobelts by microwave-ultrasonic-ultraviolet process | |
CN102942221A (en) | Method for preparing rodlike Fe4(VO4)4.5H2O microcrystal through hydrothermal synthesis | |
CN104475142A (en) | Visible-light-response doped sodium tantalum oxide and preparation method thereof | |
CN105668627A (en) | Nanometer NaBi(MoO4)2 and preparation method thereof | |
CN103332746B (en) | A kind of microwave-ultrasonic preparation h-MoO 3the method of nanometer rod | |
CN102634842B (en) | Method for preparing {001} and {100} surface-exposed anatase TiO2 nano single crystals | |
CN103145135B (en) | Method for preparing bismuth silicate nano-powder with single phase | |
CN102877130A (en) | Preparation method of bismuth ferrite BiFeO3 monocrystal micrometer sheet | |
CN103332745A (en) | Method for preparing alpha-MoO3 nanobelts by microwave-ultraviolet process | |
CN103332743A (en) | Method for preparing framework h-MoO3 nanorods by microwave-ultrasonic-ultraviolet process | |
CN103700824A (en) | Preparation method of sandwiched-layer-shaped NH4V3O8 nanocrystalline | |
CN104176759B (en) | One prepares a cube block CeO 2the molte-salt synthesis of nano material | |
CN102897818A (en) | Method for preparing Sm2O3 semiconductor nanocrystals with hexagonal sheet structures |
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 |