WO2016197181A1 - Nox gas sensor - Google Patents
Nox gas sensor Download PDFInfo
- Publication number
- WO2016197181A1 WO2016197181A1 PCT/AU2016/000199 AU2016000199W WO2016197181A1 WO 2016197181 A1 WO2016197181 A1 WO 2016197181A1 AU 2016000199 W AU2016000199 W AU 2016000199W WO 2016197181 A1 WO2016197181 A1 WO 2016197181A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tin
- gas
- gas sensor
- flakes
- sns2
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/128—Microapparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2560/00—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics
- F01N2560/02—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics the means being an exhaust gas sensor
- F01N2560/026—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics the means being an exhaust gas sensor for measuring or detecting NOx
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/0037—Specially adapted to detect a particular component for NOx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- This invention relates to gas sensors for detecting nitrogen oxides.
- Nitrogen dioxide is an industrially and biologically important gas that is mostly released during the combustion of fossil fuels. This gas can be particularly dangerous and at levels greater than 1 ppm, causing damage to the human respiration system and worsening respiratory diseases. NO2 is also a recognized air pollutant. It plays an important role in the chemistry of the atmosphere, contributing to the formation of ozone (O3), which is the major cause of photochemical smog and acid rain.
- O3 ozone
- NO2 is an important material for the synthesis of nitric acid that is used in the production of fertilisers and explosives for both military and mining uses.
- NO2 is an essential gas for many biosystems, as nitrogen monoxide (NO) appears as a gasotransmitter in many cell signalling paths can convert to NO2 rapidly in the presence of environmental perturbance.
- NOx nitrogen oxides
- the sensing of nitrogen oxides (NOx, a group mainly consists of NO2 and NO) can be potentially implemented as a diagnostic process. For instance, the detection of NOx in exhaled breath (at the ppb level) is helpful for identifying infections of lung tissus.
- the NOx can possibly be used as a biomarker for some of the gastrointestinal disorder symptoms such as irritable bowel disease (IBD).
- IBD irritable bowel disease
- the current NO2 gas sensor technologies can be categorized into
- Non-dispersive infrared sensing of NO2 is another highly selective gas sensing method (US6469303), which relies on the unique infrared light absorption fingerprint of NO2 gas molecules. Nevertheless, it needs a long enough interaction pathway between the gas molecules and infrared light beam otherwise its sensitivity will be greatly degraded. This makes them bulky and expensive. As smaller sizes, the general detection limit of these sensors is within the ppth range (part per thousand), which is not suitable for most of the applications.
- NO2 sensors are the chemiresistor type based on semiconducting metal oxides (US7704214 and US8758261), such as tin oxide (Sn02), tungsten oxide (WO3) and zinc oxide (ZnO).
- the gas diffuses into the oxide and modulates the grain boundary resistances by transferring charge carriers from the semiconductor to the adsorbed species.
- the surface affinity of these metal oxide materials is also high to gas species other than NO2, making these sensors poorly selective.
- the presence of oxygen is crucial during the operation, which will not be suitable for some particular applications with the need of oxygen-free environment such as the gastrointestinal tracts and fermentation chambers.
- the operation temperatures are usually high (> 200 °C).
- CNT carbon nanotube
- graphene US20140103330
- this invention provides a nano structured tin disulphide nitrogen oxide gas sensor.
- This nanostructured gas sensor demonstrates selectivity for NOx and can operate at temperatures below 150 °C.
- the sensor operation is based on the physisorption of nitrogen oxide on the surface of the sensitive layer.
- This invention provides a highly-selective and sensitive NO2 gas sensor based on the resistive transducing platforms using two-dimensional (2D) tin disulphide (SnS2) flakes that can operate below 150 °C.
- 2D two-dimensional tin disulphide
- the fabrication of the sensors is low-cost.
- the tin disulphide is preferably produced by reacting tin dichloride at elevated temperature with powdered sulphur in a liquid phase to form tin disulphide nano particles and separating the tin disulphide nano particles from the liquid phase.
- FIG 1 is schematic representation of the sensor of this invention
- Figure 2 illustrates the gas sensing response of 2D SnS2 flakes.
- Methods that make large surface to volume ratio are the most suitable for making gas sensors and generally two dimensional materials (2D) fall into this category.
- a 2D structure is atomically thin and the lateral dimension is much larger than this thickness.
- An example for the synthesis of 2D SnS2 is presented here.
- Tin chloride (SnCl4*5H20, 0.5 mM) can be added to a mixture of oleic acid (OAc-5 ml_) and octadecene (ODE-10 ml_) in a 100 ml_ three-neck flask to produce tin precursor.
- a standard Schlenk line can be used to protect the reaction from oxygen and moisture under a flow of high-purity N2.
- the mixed solution can be degassed at > 100 °C for a while to remove moisture and oxygen. Subsequently, the solution is stirred at elevated temperature. Then, sulphide powder can be injected into the reaction system. After cooling the solution to room temperature, the SnS2 flakes can be collected and separated from the solution by centrifugation.
- the gas sensor is shown in figure 1.
- the 2D SnS2 gas sensors are fabricated by drop-casting the solution containing 2D SnS2 flakes on the resistive transducing substrates ( Figure 1).
- the substrates are made of alumina with surface input interdigitated transducer (IDT) patterns.
- the resistance of the device is measured using a multimeter and the gas response factor is calculated using R g /R a for R g > R a , or R a /R g for R g ⁇ R a , where R a and R g represent the resistances of the device to air and the analyte gas, respectively.
- Figure 2 shows the gas sensing response of the sensor of this invention.
- b. The dynamic sensing performance of 2D SnS2 flakes toward NO2 gas with the concentrations ranged from 0.6 to 10 ppm at the operation temperature of 120 °C;
- c. The cross-talk of 2D SnS 2 flakes towards H 2 (1%), CH 4 ( 0%), CO2 (10%), H2S (56 ppm) and NO2 (10 ppm);
- d The calculated molecule-surface adsorption energies of 2D SnS2 flakes towards the aforementioned gases together with NH3.
- Table 1 The gas sensing performance of 2D SnS2 flakes toward 10 ppm N0 2 at different temperatures
- the initial response factor of the sensor at 80 °C after the exposure of 10 ppm NO2 in synthetic air balance is found to be ⁇ 28, indicating the resistance of the device after NO2 gas exposure is approximately 28 times larger than that in the presence of synthetic air.
- the surface adsorbed NO2 gas molecule acts as an electron acceptor and accepts electrons from 2D SnS2 flakes. Such a charge reduces the number of free electrons in the flake, thus increasing its resistance.
- the response factor is enhanced as well as the response and recovery time are decreased with the increase of operation temperature for up to 120 °C, suggesting that the increase of operation temperature facilitates the adsorption of NO2 gas molecules onto the 2D SnS2 surface.
- the NO2 gas sensing performance of SnS2 flakes is highly selective as only minimal responses toward other gases, including H2 (1%), CHU (10%), CO2 (10%) and H 2 S (56 ppm), are observed compared to that of NO2 (Fig. 2c).
- the closest distance between the molecules and the surface, for the bound species ranged from 2.17 to 2.87 A which is within the typical range for physisorped molecules.
- the values of the binding energies also indicate the physisorption has occurred between the molecule and the surface for CH4, CO2, H2S, NH3 and NO2, with NO2 being the most strongly bound species.
- the binding energy for NO2 is approximately 140 meV greater than for the next most bound species (NH3), while H2 and O2 are non-binding due to its relatively small adsorption energy ( ⁇ 50 meV) and positive adsorption energy (Table 3), respectively.
- FIG. 2 shows the gas sensing response of the sensor of this invention.
- the dynamic sensing performance of 2D SnS2 flakes toward NO2 gas with the concentrations ranged from 0.6 to 10 ppm at the operation temperature of 120 °C; c.
- this invention provides a gas sensor with good selectivity for nitrogen oxide gases and which is able to operate at low
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2016275551A AU2016275551A1 (en) | 2015-06-12 | 2016-06-10 | Nox gas sensor |
JP2017564481A JP2018517142A (en) | 2015-06-12 | 2016-06-10 | NOx gas sensor |
CA2989191A CA2989191A1 (en) | 2015-06-12 | 2016-06-10 | Nox gas sensor |
CN201680034236.4A CN107709228A (en) | 2015-06-12 | 2016-06-10 | NOx gas sensors |
BR112017026554A BR112017026554A2 (en) | 2015-06-12 | 2016-06-10 | nox gas sensor |
EP16806424.4A EP3307673A4 (en) | 2015-06-12 | 2016-06-10 | Nox gas sensor |
US15/735,626 US20180299395A1 (en) | 2015-06-12 | 2016-06-10 | Nox gas sensor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2015902219A AU2015902219A0 (en) | 2015-06-12 | NOx GAS SENSOR | |
AU2015902219 | 2015-06-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016197181A1 true WO2016197181A1 (en) | 2016-12-15 |
Family
ID=57502734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2016/000199 WO2016197181A1 (en) | 2015-06-12 | 2016-06-10 | Nox gas sensor |
Country Status (8)
Country | Link |
---|---|
US (1) | US20180299395A1 (en) |
EP (1) | EP3307673A4 (en) |
JP (1) | JP2018517142A (en) |
CN (1) | CN107709228A (en) |
AU (1) | AU2016275551A1 (en) |
BR (1) | BR112017026554A2 (en) |
CA (1) | CA2989191A1 (en) |
WO (1) | WO2016197181A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018183931A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with il-10 or an il-10 agonist |
WO2018183941A2 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with live biotherapeutics |
WO2018183932A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with a il-13 inhibitor |
WO2018183929A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with an immune modulatory agent released using an ingestible device |
WO2018183934A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with a chst15 inhibitor |
WO2019036363A1 (en) | 2017-08-14 | 2019-02-21 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with glatiramer or a pharmaceutically acceptable salt thereof |
WO2019232295A1 (en) | 2018-06-01 | 2019-12-05 | Progenity, Inc. | Devices and systems for gastrointestinal microbiome detection and manipulation |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111115619A (en) * | 2019-12-30 | 2020-05-08 | 深圳烯创先进材料研究院有限公司 | Preparation method of functionalized graphene with gas-sensitive performance and gas-sensitive ink |
CN112525955A (en) * | 2020-11-16 | 2021-03-19 | 深圳烯创先进材料研究院有限公司 | Graphene-based gas-sensitive material, and preparation method and application thereof |
CN112811826B (en) * | 2020-12-30 | 2022-05-20 | 西安交通大学 | SnS2Two-dimensional ordered nano-pore film, preparation method and application thereof |
CN113008945B (en) * | 2021-02-09 | 2022-08-23 | 中国石油大学(华东) | Miniature gas detection system driven by friction nano generator and preparation method and application thereof |
CN113049645A (en) * | 2021-03-15 | 2021-06-29 | 吉林大学 | Based on two-dimentional stratiform SnS2NO of nanoflower semiconductor material2Gas sensor and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104362000A (en) * | 2014-10-24 | 2015-02-18 | 南京晓庄学院 | Ultrathin SnS<2> nano-sheet, method for manufacturing same and application of ultrathin SnS<2> nano-sheet |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1590998A (en) * | 2003-09-06 | 2005-03-09 | 鸿富锦精密工业(深圳)有限公司 | Gas sensor |
-
2016
- 2016-06-10 CA CA2989191A patent/CA2989191A1/en not_active Abandoned
- 2016-06-10 AU AU2016275551A patent/AU2016275551A1/en not_active Abandoned
- 2016-06-10 EP EP16806424.4A patent/EP3307673A4/en not_active Withdrawn
- 2016-06-10 CN CN201680034236.4A patent/CN107709228A/en active Pending
- 2016-06-10 WO PCT/AU2016/000199 patent/WO2016197181A1/en active Application Filing
- 2016-06-10 BR BR112017026554A patent/BR112017026554A2/en not_active Application Discontinuation
- 2016-06-10 US US15/735,626 patent/US20180299395A1/en not_active Abandoned
- 2016-06-10 JP JP2017564481A patent/JP2018517142A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104362000A (en) * | 2014-10-24 | 2015-02-18 | 南京晓庄学院 | Ultrathin SnS<2> nano-sheet, method for manufacturing same and application of ultrathin SnS<2> nano-sheet |
Non-Patent Citations (4)
Title |
---|
GAIARDO, G. ET AL.: "Tin (IV) Sulfide chemoresistivity: A possible new gas sensing material", AISEM XVIII ANNUAL CONFERENCE, 2 February 2015 (2015-02-02), pages 1 - 4, XP032751416 * |
See also references of EP3307673A4 * |
SHI, W. ET AL.: "Hydrothermal growth and gas sensing property of flower-shaped SnS2 nanostructures", NANOTECHNOLOGY, vol. 17, 2006, pages 2918 - 2924, XP020103803 * |
XIAO, G. ET AL.: "Recent advanced in IV-VI semiconductor nanocrystals: synthesis, mechanism and applications.", ROYAL SOCIETY OF CHEMISTRY ADVANCES, vol. 3, 2013, pages 8104 - 8130, XP055333950 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018183931A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with il-10 or an il-10 agonist |
WO2018183941A2 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with live biotherapeutics |
WO2018183932A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with a il-13 inhibitor |
WO2018183929A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with an immune modulatory agent released using an ingestible device |
WO2018183934A1 (en) | 2017-03-30 | 2018-10-04 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with a chst15 inhibitor |
EP4108183A1 (en) | 2017-03-30 | 2022-12-28 | Biora Therapeutics, Inc. | Treatment of a disease of the gastrointestinal tract with an immune modulatory agent released using an ingestible device |
US11596670B2 (en) | 2017-03-30 | 2023-03-07 | Biora Therapeutics, Inc. | Treatment of a disease of the gastrointestinal tract with IL-10 or an IL-10 agonist |
WO2019036363A1 (en) | 2017-08-14 | 2019-02-21 | Progenity Inc. | Treatment of a disease of the gastrointestinal tract with glatiramer or a pharmaceutically acceptable salt thereof |
WO2019232295A1 (en) | 2018-06-01 | 2019-12-05 | Progenity, Inc. | Devices and systems for gastrointestinal microbiome detection and manipulation |
Also Published As
Publication number | Publication date |
---|---|
CA2989191A1 (en) | 2016-12-15 |
US20180299395A1 (en) | 2018-10-18 |
EP3307673A4 (en) | 2019-03-20 |
EP3307673A1 (en) | 2018-04-18 |
CN107709228A (en) | 2018-02-16 |
JP2018517142A (en) | 2018-06-28 |
BR112017026554A2 (en) | 2018-08-14 |
AU2016275551A1 (en) | 2017-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20180299395A1 (en) | Nox gas sensor | |
Ding et al. | Electrochemical detection of heavy metal ions in water | |
Zhou et al. | Humidity-enabled ionic conductive trace carbon dioxide sensing of nitrogen-doped Ti3C2T x MXene/polyethyleneimine composite films decorated with reduced graphene oxide nanosheets | |
Moon et al. | Chemiresistive electronic nose toward detection of biomarkers in exhaled breath | |
Stetter et al. | Amperometric gas sensors a review | |
Zhuiykov et al. | Development of zirconia-based potentiometric NOx sensors for automotive and energy industries in the early 21st century: What are the prospects for sensors? | |
Yamazoe | Toward innovations of gas sensor technology | |
EP2975390B2 (en) | Amperometric electrochemical gas sensing apparatus and method for measuring oxidising gases | |
US20090026076A1 (en) | Nox sensor with improved selectivity and sensitivity | |
TWI410625B (en) | Gas sensing material and gas sensor employing the same | |
Khan et al. | Recent trends in electrochemical detection of NH3, H2S and NOx gases | |
RU2509303C1 (en) | Semiconductor gas sensor | |
RU2464554C1 (en) | Gas sensor for detecting nitrogen and carbon oxides | |
US20110290672A1 (en) | Electrochemical gas sensor | |
Yang et al. | Promoting selectivity and sensitivity for a high temperature YSZ-based electrochemical total NOx sensor by using a Pt-loaded zeolite Y filter | |
US20170016847A1 (en) | Amperometric electrochemical gas sensing apparatus and method for measuring oxidising gases | |
CN108535346A (en) | The solid electrolyte type carbon dioxide sensor for being influenced to reduce by volatile organic compounds | |
WO2019049693A1 (en) | Formaldehyde detecting sensor and system employing same | |
Li et al. | Label-free electrochemiluminescence immunosensor based on Ce-MOF@ g-C3N4/Au nanocomposite for detection of N-terminal pro-B-type natriuretic peptide | |
Lee et al. | The sensing behavior of SnO2-based thick-film gas sensors at a low concentration of chemical agent simulants | |
Suetsugu et al. | C3H6 sensing characteristics of rod-type yttria-stabilized zirconia-based sensor for ppb level environmental monitoring applications | |
EP3893748B1 (en) | Hydrogen breath analyzer and breath test method | |
Nirbhaya et al. | 3D-phosphorus doped mesoporous graphitic carbon nitride based immunosensor for swine flu detection | |
RU2583166C1 (en) | Semiconductor gas sensor | |
JP6360373B2 (en) | Sensor and structure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16806424 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017564481 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2989191 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15735626 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2016275551 Country of ref document: AU Date of ref document: 20160610 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2016806424 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112017026554 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112017026554 Country of ref document: BR Kind code of ref document: A2 Effective date: 20171208 |