CN105444911A - Doped strontium titanate film thermocouple - Google Patents

Doped strontium titanate film thermocouple Download PDF

Info

Publication number
CN105444911A
CN105444911A CN201510771506.7A CN201510771506A CN105444911A CN 105444911 A CN105444911 A CN 105444911A CN 201510771506 A CN201510771506 A CN 201510771506A CN 105444911 A CN105444911 A CN 105444911A
Authority
CN
China
Prior art keywords
film
strontium titanate
doping
thermodes
thermode
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.)
Pending
Application number
CN201510771506.7A
Other languages
Chinese (zh)
Inventor
史鹏
任巍
田边
蒋庄德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN201510771506.7A priority Critical patent/CN105444911A/en
Publication of CN105444911A publication Critical patent/CN105444911A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
    • G01K7/04—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples the object to be measured not forming one of the thermoelectric materials

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to a doped strontium titanate film thermocouple. Two differently-doped strontium titanate films are adopted as thermal electrode materials of the thermocouple, and a doped strontium titanate oxide film thermocouple is prepared through deposition on a high-temperature ceramic substrate by use of a magnetron sputtering, silk screen printing or chemical spin coating process. The film thermocouple is directly surface-mounted or coated on the surface of the ceramic substrate, can be used for temperature measurement in a high-temperature oxidizing atmosphere, and can work stably for a long time at high temperature of 1200-1500 DEG C.

Description

A kind of strontium titanate doping film-type thermopair
[technical field]
The present invention relates to sensor technology of preparing and high-temperature temperature field of measuring technique, be specially a kind of strontium titanate doping film-type thermopair.
[background technology]
In Aeroengine Design and confirmatory experiment, in order to the design of the burning efficiency and cooling system of verifying engine, need the temperature at the positions such as accurate test engine turbine blade surface, Inner Wall of Combustion Chamber.Linearly to compare with block shape thermopair with traditional, refractory ceramics type film thermocouple has the features such as thermal capacity is little, volume is little, fast response time, transient temperature change can be caught, film thermocouple can be directly deposited on the surface of measurand simultaneously, do not destroy unit under test structure, and little on the impact of unit under test working environment.Therefore be more suitable for for surface transient temperature measuring.Hot-end component surface temperature distribution situation accurately can be understood by film thermocouple, heat transfer, cooling scheme design can be optimized, and then ensure that engine operation is in optimum duty, raising engine efficiency, for the design of new-generation fighter and airline carriers of passengers provides reliable basis.
Research at present to NiCr/NiSi film thermocouple, relative maturity, but its Range of measuring temp is low, only adapts to test occasion with medium and low temperature.In high temperature test field, usually adopt the noble metal such as platinum, rhodium to be membraneous material, but there is the problems such as cost is high, error is large, rugged surroundings are oxidizable due to it.In the urgent need to developing a kind of new ceramics film thermocouple of high temperature resistant, stable performance.In existing research, ITO and In of film-type 2o 3material is expected to become pyrometric core preferred material.But further study discovery, ITO series thin film thermopair owing to there will be very violent heat volatilization at the high-temperature area being greater than 1000 DEG C, thus causes the restriction of its pyrometric instability and maximum temperature.This point seriously governs the application of ito thin film in the contour temperature measurement field of high-temperature hot runner.
SrTiO 3as the typical N-shaped oxide pyroelectric material of one, there is environmental friendliness and the advantage such as to have stable high-temperature performance, good electronic conductor can be become by doping high valence ion, become now a kind of very useful high-temperature thermoelectric material be familiar with by everybody.If by the strontium titanate doping thermoelectric material of two kinds of different conductive characteristics by reasonably combination, just likely become a kind of new high temperature modification film thermocouple.This is this starting point of inventing just.
[summary of the invention]
The present invention be directed to the feature of current material system and higher application demand, provide a kind of strontium titanate doping film-type thermopair, for the high temperature measurement demand of extreme environment.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of strontium titanate doping film-type thermopair, comprise setting two thermodes on a ceramic substrate, the material of two thermodes is respectively the strontium titanate film of two kinds of different element dopings; Or the material of two thermodes is the strontium titanate film of same element doping, and in two thermodes, element doping content is different.
Doped chemical is La, Nb, Sc, Ca, Al, In, Ce, Dy, Zn or Mn.
The content of doped chemical is 0.1-15%mol.
When the strontium titanate film of same element doping is as two thermode materials, in two thermode materials, element doping content gets the maximum doping of this element in strontium titanates and minimum doping respectively.
Described two thermodes are that specular is arranged along ceramic substrate center line, and two thermodes overlap joint forms U-shaped structures or V-structure.
The length of each thermode is at 8-30cm, and width is 0.2-1.55cm, and thickness is 0.3-20 μm, and the length in two thermode overlap joint coincidence districts is 0.5-3cm.
Described ceramic substrate is the structural ceramics of aluminium oxide, mullite or SiC.
Two described thermodes adopt magnetron sputtering, serigraphy, pulsed laser deposition or chemical solution method, are deposited as film-type thermode on a ceramic substrate, then obtain through 600-1100 DEG C of thermal treatment.
Relative to prior art, the present invention has the following advantages:
The present invention be directed to the feature of current material system and higher application demand, research and design is applicable to film thermocouple of refractory ceramics substrate and preparation method thereof.Utilize the high Seebeck coefficient characteristic of material doped modified the showed excellence of strontium titanate film, the film of two kinds of different conductive characteristics is adopted to form film-type thermopair, by magnetron sputtering, serigraphy or chemical spin coating proceeding, strontium titanate doping sull is prepared at refractory ceramics deposition on substrate, the film-type thermopair at high temperature stablizing output signal is finally obtained again, for the high temperature measurement demand of extreme environment through high-temperature heat treatment.This film thermocouple adopt directly mount or be coated in ceramic substrate surface, can be used for the temperature survey in high temperature oxidative atmosphere, can under 1200 DEG C of-1500 DEG C of high temperature long-term stable operation.The present invention adopts new ceramics thermocouple material, compares common K type thermopair, has temperature-measuring range wider, and can adapt to the advantage of oxidation and acid or alkali environment; Compare other types high temperature resisting thermocouple material as platinum rhodium etc., within the scope of identical temperature test, its thermopair cost is low; Compared to ceramic membrane thermopairs such as conventional I TO, there is higher serviceability temperature and longer high-temperature service time, and be applicable to the extreme ambient temperature test in fields such as space flight and aviation.
[embodiment]
The two group thermode materials of strontium titanate film as film thermocouple of two kinds of different doping chosen by a kind of strontium titanate doping film-type thermopair of the present invention, can be identity element doping, but content are different; Also can be single doping and the codope of different component elements.Doped chemical is mainly La, Nb, Sc, Ca, Al, Ce, Dy, In, Zn, Mn etc.Then, according to the doping component designed, adopt magnetron sputtering, serigraphy or chemical spin coating proceeding, can be used for the sull thermopair of high-temperature temperature measurement in the preparation of refractory ceramics deposition on substrate, and adopt pattern technology to form the device architecture with thermocouple structure feature.Thermopair can be graphically V-type or U-shaped, consist of the coincidence district, hot junction of film thermocouple between two thermodes part overlapping region, the length in coincidence district is between 0.5-3cm.In film thermocouple, the thickness of thermode is in 0.3-20 micrometer range, and the length of thermode is between 8-30cm, and the width of each thermode is 0.2-1.55cm.Finally, by the film thermocouple for preparing at 600-1100 DEG C of high-temperature heat treatment 1-3 hour, improve the density of film.Final acquisition can at the sull type thermopair of steady operation under high temperature oxidative atmosphere.
According to stechiometry, the chemical formula formed after various element doping is:
La part replaces SrLa xsr 1-xtiO 3;
Al part replaces TiSrAl xti 1-xo 3;
Ce part replaces SrCe xsr 1-xtiO 3;
In part replaces TiSrIn xti 1-xo 3;
Sc part replaces SrSc xsr 1-xtiO 3;
Ca part replaces SrCa xsr 1-xtiO 3;
Zn part replaces SrZn xsr 1-xtiO 3;
Mn part replaces SrMn xsr 1-xtiO 3;
Nb part replaces TiSrNb xti 1-xo 3;
Replace Sr time Dy content is little, replace Sr and Ti when content is higher, Dy simultaneously xsr 1-xdy yti 1-yo 3;
Principle of the present invention: Seebeck (Seebeck) effect, also known as work first thermoelectric effect, it refers to temperature contrast due to two kinds of different electric conductors or semiconductor and causes the pyroelectric phenomena of the voltage difference between two kinds of materials.And Seebeck coefficient S is the material characteristic based on temperature, know the Seebeck coefficient S (T) of a material, transform the voltage difference can learnt between two thermodes from formula, thus indirectly can obtain the temperature difference of cold and hot section.
Δ V = ∫ T 1 T 2 S d T
Wherein, E fOfor Fermi's energy during 0K.As can be seen from formula above, along with the rising of temperature, the energy in Fermi distribution function also rises fast, so every averaged electron energy of heating end is higher, accordingly, the electronics of heating end is constantly dispersed to cold section, stops it to disperse further until form a voltage difference.Can show that the expression formula of Seebeck coefficient is further by mathematical derivation: as can be seen from formula, Seebeck coefficient can be relevant, also relevant with actual kelvin rating with the Fermi of material itself.So, for two groups of thermode materials, if cold hot-side temperature is determined, the temperature difference between them and voltage difference are exactly fixing.This is just as the necessary basic demand of high temperature modification thermopair.Equally, appreciable thermoelectrical potential difference will be formed at the cold forging of two thermodes when the Seebeck coefficient of two thermode materials is inconsistent.
SrTiO 3as the typical N-shaped oxide pyroelectric material of one, there is environmental friendliness and the advantage such as to have stable high-temperature performance, good electronic conductor can be become by doping high valence ion.What show especially under the high temperature conditions is particularly outstanding.Meanwhile, cause electric property to change due to carrier scattering mechanism change after adulterating, Fermi level and the intrinsic Seebeck coefficient of material all change.Therefore, we select the two group thermode materials of strontium titanate films as film thermocouple of two kinds of different doping, and just can form can the film-type thermopair of at high temperature steady operation.
Below in conjunction with the present invention will be further described with specific embodiment, the invention is not restricted to following examples.
Embodiment 1
Choose the two group thermode materials of strontium titanate film as film thermocouple of La, Nb two kinds of different element dopings, doping content is 1%, be denoted as LST1 and NST1 respectively, adopt magnetron sputtering technique at thickness be 2mm alumina substrate on carry out deposition and the preparation of film.First, synthesize and the sputtering of the identical oxide ceramics target of design component for film.By sputtering pressure (5Pa), O2 to Ar ratio (1:6) and sputtering power (120w) in adjustment sputtering technology, sputter 8 hours and obtain that thickness is 5 microns, the length of thermode is 20cm, the width of thermode is 0.6cm, have the LST1-NST1 film-type thermopair of U-shaped structure, between two thermodes, coincidence section length in hot junction is 1.5cm.Finally, by the film thermocouple for preparing 800 DEG C of thermal treatments 3 hours, final acquisition can at the sull type thermopair of steady operation under high temperature oxidative atmosphere.
Embodiment 2
Choose the two group thermode materials of strontium titanate film as film thermocouple of Dy, Nb two kinds of different element dopings, doping content is respectively 5% and 2%, be denoted as DST5 and NST2 respectively, adopt magnetron sputtering technique at thickness be 5mm alumina substrate on carry out deposition and the preparation of film.First, synthesize and the sputtering of the identical oxide ceramics target of design component for film.By sputtering pressure (10Pa), O2 to Ar ratio (1:4) and sputtering power (150w) in adjustment sputtering technology, sputter 7 hours and obtain that thickness is 5 microns, the length of thermode is 15cm, the width of thermode is 0.5cm, have the DST5-NST2 film-type thermopair of U-shaped structure, between two thermodes, coincidence section length in hot junction is 1.5cm.Finally, by the film thermocouple for preparing 850 DEG C of thermal treatments 2.5 hours, final acquisition can at the sull type thermopair of steady operation under high temperature oxidative atmosphere.
Embodiment 3
Choose the two group thermode materials of strontium titanate film as film thermocouple of La, Ca two kinds of different element dopings, doping content is respectively 5% and 10%, is denoted as LST5 and CST10 respectively, adopts chemical solution deposition technique to carry out deposition and the preparation of film.First, synthesize respectively and meet mixing La and mixing the strontium titanates precursor sol liquid solution (solution concentration is 0.4mol/L) of Ca of stoichiometric proportion, adopt spin coating proceeding to carry out the preparation of film.LST5 film is prepared in first spin coating, and then prepares CST10 film.The spin coating rotating speed of setting film is 2500rpm, the wet film that each spin coating obtains successively repeats spin-on deposition in 400 DEG C of dryings 5 minutes, 650 DEG C of thermal treatments after 10 minutes again, each thermode all repeats 15 times, acquisition thickness is 1 micron, the length of thermode is 10cm, the width of thermode is 0.3cm, have the LST5-CST10 film-type thermopair of U-shaped structure, between two thermodes, coincidence section length in hot junction is 1.2cm.Finally, by the film thermocouple for preparing 900 DEG C of thermal treatments 4 hours, final acquisition can at the sull type thermopair of steady operation under high temperature oxidative atmosphere.
Embodiment 4
Choose the two group thermode materials of strontium titanate film as film thermocouple of La, Nb two kinds of different element dopings, doping content is respectively 5% and 2%, be denoted as LST5 and NST2 respectively, adopt silk-screen printing technique at thickness be 3mm aluminium oxide ceramic substrate on deposit film thermode.Ceramic size for serigraphy is made up of the ceramic powder mixed La strontium titanates (LST5) and mix Nb strontium titanates (NST2) meeting stoichiometric proportion respectively.The granularity of powder is 100nm, adopts the mixed solution of ethyl cellulose and terpinol 1:2 as organic solvent, to be joined in organism by ceramic powder and carry out strong stirring mixing, as the ceramic size for serigraphy according to the ratio of 1:1.Choosing thermode length is 25cm, and width is 0.8cm, and the U-shaped structure mask plate of hot junction coincidence head of district 1.5cm carries out the serigraphy preparation of film thermal electrode, and half tone used is 200 orders.First on substrate, print LST5 film, and then print NST2 film, after two kinds of membraneous materials all deposit and terminate, by film sample 1100 DEG C of thermal treatment 4 hours in muffle furnace, programming rate remains on 3 DEG C/min, finally prepares the strontium titanate doping film-type thermopair with U-shaped structure that film thickness is 20 microns.
Embodiment 5
Choose the two group thermode materials of strontium titanate film as film thermocouple of two groups of Different L a doping contents, doping content is respectively 1% and 15%, is denoted as LST1 and LST15 respectively, adopts magnetron sputtering technique to carry out deposition and the preparation of film.First, synthesize and the sputtering of the identical oxide ceramics target of design component for film.By sputtering pressure (5Pa), O2 to Ar ratio (1:4) and sputtering power (150w) in adjustment sputtering technology, sputter 8 hours and obtain that thickness is 5 microns, the length of thermode is 20cm, the width of thermode is 0.6cm, have the LST1-LST15 film-type thermopair of U-shaped structure, between two thermodes, coincidence section length in hot junction is 1.5cm.Finally, by the film thermocouple for preparing 1000 DEG C of thermal treatments 3 hours, final acquisition can at the sull type thermopair of steady operation under high temperature oxidative atmosphere.

Claims (8)

1. a strontium titanate doping film-type thermopair, is characterized in that, comprise setting two thermodes on a ceramic substrate, the material of two thermodes is respectively the strontium titanate film of two kinds of different element dopings; Or the material of two thermodes is the strontium titanate film of same element doping, and in two thermodes, element doping content is different.
2. a kind of strontium titanate doping film-type thermopair according to claim 1, it is characterized in that, doped chemical is La, Nb, Sc, Ca, Al, In, Ce, Dy, Zn or Mn.
3. a kind of strontium titanate doping film-type thermopair according to claim 1, is characterized in that, the content of doped chemical is 0.1-15%mol.
4. a kind of strontium titanate doping film-type thermopair according to claim 3, it is characterized in that, when the strontium titanate film of same element doping is as two thermode materials, in two thermode materials, element doping content gets the maximum doping of this element in strontium titanates and minimum doping respectively.
5. a kind of strontium titanate doping film-type thermopair according to claim 1, is characterized in that, described two thermodes are that specular is arranged along ceramic substrate center line, and two thermodes overlap joint forms U-shaped structures or V-structure.
6. a kind of strontium titanate doping film-type thermopair according to claim 4, is characterized in that, the length of each thermode is at 8-30cm, and width is 0.2-1.55cm, and thickness is 0.3-20 μm, and the length in two thermode overlap joint coincidence districts is 0.5-3cm.
7. a kind of strontium titanate doping film-type thermopair according to claim 1, it is characterized in that, described ceramic substrate is the structural ceramics of aluminium oxide, mullite or SiC.
8. a kind of strontium titanate doping film-type thermopair according to claim 1, it is characterized in that, two described thermodes adopt magnetron sputtering, serigraphy, pulsed laser deposition or chemical solution method, be deposited as film-type thermode on a ceramic substrate, then obtain through 600-1100 DEG C of thermal treatment.
CN201510771506.7A 2015-11-12 2015-11-12 Doped strontium titanate film thermocouple Pending CN105444911A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510771506.7A CN105444911A (en) 2015-11-12 2015-11-12 Doped strontium titanate film thermocouple

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510771506.7A CN105444911A (en) 2015-11-12 2015-11-12 Doped strontium titanate film thermocouple

Publications (1)

Publication Number Publication Date
CN105444911A true CN105444911A (en) 2016-03-30

Family

ID=55555373

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510771506.7A Pending CN105444911A (en) 2015-11-12 2015-11-12 Doped strontium titanate film thermocouple

Country Status (1)

Country Link
CN (1) CN105444911A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105823569A (en) * 2016-04-27 2016-08-03 西安交通大学 Lanthanum chromite-doped film type thermocouple and preparation method thereof
CN106595894A (en) * 2016-12-19 2017-04-26 美的集团股份有限公司 Thin film thermocouple and temperature sensing device equipped with thin film thermocouple
CN110407156A (en) * 2018-04-28 2019-11-05 华中科技大学 A method of thick film thermocouple is prepared in three-dimensional surface based on laser direct-writing technique
CN115869935A (en) * 2021-09-30 2023-03-31 丰田自动车株式会社 Semiconductor particles for water-splitting photocatalyst, photocatalyst formed of semiconductor particles, and synthesis method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
孙毅: "氧化物热电材料的制备及性能研究", 《中国博士学位论文全文数据库》 *
贾石峰等: "《传感器原理与传感器技术》", 30 September 2009 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105823569A (en) * 2016-04-27 2016-08-03 西安交通大学 Lanthanum chromite-doped film type thermocouple and preparation method thereof
CN106595894A (en) * 2016-12-19 2017-04-26 美的集团股份有限公司 Thin film thermocouple and temperature sensing device equipped with thin film thermocouple
CN110407156A (en) * 2018-04-28 2019-11-05 华中科技大学 A method of thick film thermocouple is prepared in three-dimensional surface based on laser direct-writing technique
CN110407156B (en) * 2018-04-28 2022-01-07 华中科技大学 Method for preparing thick-film thermocouple on three-dimensional surface based on laser direct writing process
CN115869935A (en) * 2021-09-30 2023-03-31 丰田自动车株式会社 Semiconductor particles for water-splitting photocatalyst, photocatalyst formed of semiconductor particles, and synthesis method thereof

Similar Documents

Publication Publication Date Title
CN105823569B (en) A kind of doping chromic acid lanthanum film type thermocouple and preparation method thereof
CN105444911A (en) Doped strontium titanate film thermocouple
CN105300544B (en) A kind of sull type thermocouple and preparation method thereof
Shi et al. Effects on structure and properties of BCZT lead-free piezoelectric ceramics by rare-earth doping
CN110042355A (en) A kind of film thermocouple and its manufacturing method with one-dimensional nano-array structure
CN110903087A (en) Low-B high-resistance wide-temperature-zone high-temperature thermistor material and preparation method and application thereof
Li et al. Fast response and high stability Mn–Co–Ni–Al–O NTC microbeads thermistors
Chung et al. Low-temperature-sintered Pr-doped 0.93 (Bi0. 5Na0. 5) TiO3-0.07 BaTiO3 multifunctional ceramics with Li2CO3 sintering aid
Pradhani et al. Structural, impedance, and leakage current characteristics of stannum modified Bi 0.5 Na 0.5 TiO 3 ceramic
CN103664173B (en) A kind of preparation method of high-temperature thick-film thermistor
CN105294074B (en) A kind of method that use silk-screen printing technique prepares sull type thermocouple
Kumar et al. Investigation on energy storage properties and thermally stable dielectric constant for high temperature electronic device applications in the holmium substituted Na 0.5 Bi 0.5 TiO 3
Zhang et al. Large electric-induced pyroelectric properties in (Pb0. 87La0. 02Ba0. 1)(Zr0. 7Sn0. 24Ti0. 06) O3 antiferroelectric ceramics with excess PbO
CN106679838B (en) Film type thermocouple with super-large output voltage and preparation method thereof
Liu et al. Investigation on thermoelectric properties of screen-printed La1-xSrxCrO3-In2O3 thermocouples for high temperature sensing
Khetre et al. Electrical and dielectric properties of nanocrystalline LaCrO 3
Kunej et al. Sol–Gel Synthesis and Characterization of Na 0.5 Bi 0.5 TiO 3–NaTaO 3Thin Films
JP4457215B2 (en) Tube material with thermoelectric power generation function
Ge et al. Oxygen vacancies-related high-temperature dielectric relaxation and pyroelectric energy harvesting in lead-free Ba (Zr 0.2 Ti 0.8) O 3 ceramics
JP2004093547A (en) Resistance type oxygen sensor, oxygen sensor system, and air-fuel ratio control system using the same
Lou et al. Structure, dielectric properties and impedance analysis of lead-free (1− x) Na 0.5 Bi 0.5 TiO 3-x SrTiO 3 ceramics
Lee et al. Bi (Zn0. 5Ti0. 5) O3 substitution effects in Pb (Zr, Ti) O3 piezoelectric ceramics around morphotropic phase boundary region
Ji et al. Formation of highly textured Zn0. 2Ni0. 8Mn2O4 thin films by RF magnetron sputtering
Siskandar et al. Ferroelectric sensor BaxSr1-xTiO3 integrated with android smartphone for controlling and monitoring smart street lighting
US5864148A (en) High-temperature gas sensor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160330

WD01 Invention patent application deemed withdrawn after publication