CN105314976A - Ti-based low loss K value microwave dielectric ceramic and preparation method thereof - Google Patents

Ti-based low loss K value microwave dielectric ceramic and preparation method thereof Download PDF

Info

Publication number
CN105314976A
CN105314976A CN201510772208.XA CN201510772208A CN105314976A CN 105314976 A CN105314976 A CN 105314976A CN 201510772208 A CN201510772208 A CN 201510772208A CN 105314976 A CN105314976 A CN 105314976A
Authority
CN
China
Prior art keywords
loss
low
preparation
medium ceramics
microwave
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
Application number
CN201510772208.XA
Other languages
Chinese (zh)
Other versions
CN105314976B (en
Inventor
周迪
李文博
赵金雄
姚熹
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.)
Suzhou Academy of Xian Jiaotong University
Original Assignee
Suzhou Academy of 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 Suzhou Academy of Xian Jiaotong University filed Critical Suzhou Academy of Xian Jiaotong University
Priority to CN201510772208.XA priority Critical patent/CN105314976B/en
Publication of CN105314976A publication Critical patent/CN105314976A/en
Application granted granted Critical
Publication of CN105314976B publication Critical patent/CN105314976B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a Ti-based low loss K value microwave dielectric ceramic and a preparation method thereof. The formula of the chemical structure of the ceramic is (1+0.7x)TiO2-(1-x)CoO-0.1xNb2O5-0.1xCuO, wherein x is not smaller than 0.8 and not larger than 0.9. The ceramic provided by the invention is higher in relative dielectric constant, good in microwave performance, adjustable in temperature coefficient of resonance frequency, and is simple in chemical composition and preparation method.

Description

K value microwave-medium ceramics and preparation method thereof in the low-loss of Ti base
Technical field
The present invention relates to K value microwave-medium ceramics and preparation method thereof in the low-loss of a kind of Ti base, belong to technical field of electronic ceramic.
Background technology
Microwave-medium ceramics is the new function electronic ceramics developed rapidly over nearly 30 years, and it has, and loss is low, frequency-temperature coefficient is little, specific inductivity high.Dielectric resonator (DielectricResonator is called for short DR), dielectric filter, duplexer, microwave-medium antenna, dielectric resonator oscillator (claiming DRO), Medium Wave Guide transmission line etc. can be made with microwave ceramic material.Microwave-medium ceramics extremely catches people's attention at modern communications, military technological field etc.Microwave current device is to highly integrated, and miniaturization, high reliability and cost degradation future development, as microwave dielectric material, it has high-k, low Jie's loss of electrons, low-temperature coefficient.The production level of microwave current stupalith and device is the highest with the company such as day Murata company, moral EPCOS company, beautiful Trans-Tech company, NardaMICROWAVE-WEST company, English MorganElectroCeramics, Filtronic.The range of application of its product is in 300MHz ~ 40GHz seriation, and annual value of production all reaches more than 1,000,000,000 dollars.The production of domestic microwave dielectric ceramic materials and device, has larger gap at state of the art, range of product with in industrial scale compared with abroad.The fields such as dielectric resonator, wave filter, Medium Wave Guide, medium substrate and medium Meta Materials are widely used in along with microwave-medium ceramics, therefore, in searching, preparation, the Novel microwave dielectric ceramic of high-k, low-loss, near-zero resonance frequency temperature coefficient, low cost, environmental protection becomes focus and the emphasis of people's current research.
Summary of the invention
The present invention seeks to: for the problems referred to above, there is provided K value microwave-medium ceramics and preparation method thereof in the low-loss of a kind of Ti base, this stupalith relative permittivity is higher, and microwave property is good, temperature coefficient of resonance frequency is adjustable, chemical constitution and preparation method simple.
Technical scheme of the present invention is: K value microwave-medium ceramics in this Ti base provided by the present invention low-loss, and its chemical structure expression formula is (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5-0.1xCuO, wherein 0.8≤x≤0.9.
The method of K value microwave-medium ceramics in the low-loss of this preparation provided by the present invention above-mentioned Ti base, it comprises the following steps:
1) by copper, cobalt, niobium and titanyl compound according to (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5mix after the molar ratio weighing of-0.1xCuO, wherein 0.8≤x≤0.9, then abundant ball milling, ball milling post-drying, sieve and be pressed into blocks, then at 1150 DEG C, be incubated 4.5h, obtain sample and burn block;
2) by above-mentioned steps 1) sample that obtains burns block and pulverizes, then abundant ball milling, ball milling post-drying, granulation, sieves, by the particle compression moulding after sieving, then at 1200 DEG C ~ 1320 DEG C, sinter 2h become porcelain, obtain K value microwave-medium ceramics in the low-loss of Ti base.
This preparation method of the present invention, on the basis of technique scheme, also comprises following preferred version:
Described copper, cobalt, niobium and titanyl compound are respectively CuO, Co 2o 3, Nb 2o 5, and TiO 2.
In described step 1) and step 2) ball milling operation in, Ball-milling Time is 4h ~ 5h.
In described step 1) and step 2) baking operation in, bake out temperature is 100 ~ 120 DEG C.
In described step 1) sieve in operation, adopt 120 object screen clothes; In described step 2) sieve in operation, adopt bilayer to sieve technique, cross 60 orders and 120 object screen clothes respectively.
In described step 2) in, described granulation refers to the aqueous solution by powder and polyvinyl alcohol, then makes micron-sized spheroidal particle.
In described step 2) in, described sintering is the sintering under air atmosphere.
In described step 2) in, described compression moulding is pressed into bulk or cylindric.
Compared with prior art, the present invention has following useful technique effect:
1, K value microwave-medium ceramics in the low-loss of this Ti base of the present invention, to be rich in the Rutile Type of Ti element and Perovskite Phase for pivot, sinters at 1200 DEG C ~ 1320 DEG C.The present invention is relevant with dielectric medium theoretical according to morphology, basis is complex as with the Perovskite Phase of the Rutile Type of Cu, Nb and Ti composition and Co, Ti composition, by suitable ceramic process, can sinter out fine and close in air atmosphere and possess the new function pottery (forming the ceramic of compact of Rutile Type and Perovskite Phase two-phase compound) of excellent microwave dielectric property, this kind of pottery can use as the dielectric material such as radio frequency laminated ceramic capacitor, chip microwave dielectric resonator or wave filter, ceramic antenna, mcm (MCM).
2, in Ti base of the present invention low-loss, K value microwave dielectric ceramic materials has following characteristics: relative permittivity is adjustable (27.5 ~ 35.2), good (the Qf=34 of microwave property, 410GHz ~ 37,450GHz), temperature coefficient of resonance frequency nearly zero and easy-regulating (-9.5ppm/ DEG C ~+31ppm/ DEG C), chemical constitution and preparation technology simple.
Prepared by the method that 3, present invention employs the most simple and effective solid state reaction sintering, first be the formula choosing proper ratio, choose suitable initial oxide, by a ball milling, various oxide compound is mixed, oxide compound is made to carry out preliminary reaction by presintering process, by the particle size of secondary ball milling refinement reactant, obtain required ceramics sample finally by sintering process.By a kind of so simple effective preparation method, the specific inductivity of the ceramics sample obtained changes between 27.5 ~ 35.2 with composition, Qf is distributed in 34,410GHz ~ 37,450GHz, temperature coefficient of resonance frequency nearly zero and easy-regulating (-9.5ppm/ DEG C ~+31ppm/ DEG C), sintering temperature 1200 DEG C ~ 1320 DEG C.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Embodiment 1:
First by raw material CuO, Co of purity assay 2o 3, Nb 2o 5and TiO 2according to formula general formula (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5after molar ratio in-0.1xCuO (wherein x=0.8), abundant mixing and ball milling (200 revs/min) 4 hours, then dry at 120 DEG C, cross 120 objects sieves, briquetting, through 1150 DEG C of insulations 4.5 hours under air atmosphere, obtain sample and burn block.
Then the sample obtained is burnt after block is pulverized and carry out secondary ball milling again, Ball-milling Time is 5 hours, granulation after drying at 120 DEG C is (by the aqueous solution of powder and polyvinyl alcohol, then micron-sized spheroidal particle is made), sieve through 60 orders and 120 eye mesh screen bilayers, required porcelain can be obtained; By porcelain compression moulding on demand (being usually pressed into block or cylindric), under 1200 DEG C of air, then sintering 2h become porcelain, namely obtain the finished product of K value microwave-medium ceramics in the low-loss of Ti base.
K value microwave-medium ceramics in Ti base low-loss obtained by the present embodiment, its chemical constitution can be expressed as (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5-0.1xCuO, wherein x=0.8.
After tested, the performance of the stupalith obtained by the present embodiment reaches following index:
Porcelain is sintered into, the dielectric properties ε under microwave in 1200 DEG C of air r=35.2 (5.06GHz), quality factor q=6800, Qf=34,410GHz, temperature coefficient of resonance frequency TCF=+31ppm/ DEG C (25 DEG C ~ 85 DEG C) under microwave.
Embodiment 2:
First by raw material CuO, Co of purity assay 2o 3, Nb 2o 5and TiO 2according to formula general formula (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5after molar ratio in-0.1xCuO (wherein x=0.85), abundant mixing and ball milling (200 revs/min) 4 hours, then dry at 120 DEG C, cross 120 objects sieves, briquetting, through 1150 DEG C of insulations 4.5 hours under air atmosphere, obtain sample and burn block.
Then the sample obtained is burnt after block is pulverized and carry out secondary ball milling again, Ball-milling Time is 5 hours, granulation after drying at 120 DEG C is (by the aqueous solution of powder and polyvinyl alcohol, then micron-sized spheroidal particle is made), sieve through 60 orders and 120 eye mesh screen bilayers, required porcelain can be obtained; By porcelain compression moulding on demand, under 1220 DEG C of air, then sinter 2h become porcelain, namely obtain the finished product of K value microwave-medium ceramics in the low-loss of Ti base.
K value microwave-medium ceramics in Ti base low-loss obtained by the present embodiment, its chemical constitution can be expressed as (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5-0.1xCuO, wherein x=0.85.
After tested, the performance of the stupalith obtained by the present embodiment reaches following index:
Porcelain is sintered into, the dielectric properties ε under microwave in 1220 DEG C of air r=31.3 (5.036GHz), quality factor q=7000, Qf=35,250GHz, temperature coefficient of resonance frequency TCF=+11ppm/ DEG C (25 DEG C ~ 85 DEG C) under microwave.
Embodiment 3:
First by raw material CuO, Co of purity assay 2o 3, Nb 2o 5and TiO 2according to formula general formula (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5after molar ratio in-0.1xCuO (wherein x=0.87), abundant mixing and ball milling (200 revs/min) 4 hours, then dry at 120 DEG C, cross 120 objects sieves, briquetting, through 1150 DEG C of insulations 4.5 hours under air atmosphere, obtain sample and burn block;
Then the sample obtained is burnt after block is pulverized and carry out secondary ball milling again, Ball-milling Time is 5 hours, granulation after drying at 120 DEG C is (by the aqueous solution of powder and polyvinyl alcohol, then micron-sized spheroidal particle is made), sieve through 60 orders and 120 eye mesh screen bilayers, required porcelain can be obtained; By porcelain compression moulding on demand, under 1280 DEG C of air, then sinter 2h become porcelain, namely obtain K value microwave-medium ceramics in the low-loss of Ti base.
K value microwave-medium ceramics in Ti base low-loss obtained by the present embodiment, its chemical constitution can be expressed as (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5-0.1xCuO, wherein x=0.87.
After tested, the performance of the stupalith obtained by the present embodiment reaches following index:
Porcelain is sintered into, the dielectric properties ε under microwave in 1280 DEG C of air r=29.5 (5.108GHz), quality factor q=7000, Qf=36,780GHz, temperature coefficient of resonance frequency TCF=+2.6ppm/ DEG C (25 DEG C ~ 85 DEG C) under microwave.
Embodiment 4:
First by raw material CuO, Co of purity assay 2o 3, Nb 2o 5and TiO 2according to formula general formula (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5after molar ratio in-0.1xCuO (wherein x=0.9), abundant mixing and ball milling (200 revs/min) 4 hours, then dry at 120 DEG C, cross 120 objects sieves, briquetting, through 1150 DEG C of insulations 4.5 hours under air atmosphere, obtain sample and burn block;
Then the sample obtained is burnt after block is pulverized and carry out secondary ball milling again, Ball-milling Time is 5 hours, granulation after drying at 120 DEG C is (by the aqueous solution of powder and polyvinyl alcohol, then micron-sized spheroidal particle is made), sieve through 60 orders and 120 eye mesh screen bilayers, required porcelain can be obtained; By porcelain compression moulding on demand, under 1320 DEG C of air, then sinter 2h become porcelain, namely obtain K value microwave-medium ceramics in the low-loss of Ti base.
K value microwave-medium ceramics in Ti base low-loss obtained by the present embodiment, its chemical constitution can be expressed as (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5-0.1xCuO, wherein x=0.9.
After tested, the performance of the stupalith obtained by the present embodiment reaches following index:
Porcelain is sintered into, the dielectric properties ε under microwave in 1320 DEG C of air r=27.5 (5.312GHz), quality factor q=7050, Qf=37,450GHz, temperature coefficient of resonance frequency TCF=-9.5ppm/ DEG C (25 DEG C ~ 85 DEG C) under microwave.
Certainly, above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to people can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to the spirit of main technical schemes of the present invention or modification, all should be encompassed within protection scope of the present invention.

Claims (9)

1. a K value microwave-medium ceramics in the low-loss of Ti base, is characterized in that: the chemical structure expression formula of this pottery is (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5-0.1xCuO, wherein 0.8≤x≤0.9.
2. the preparation method of K value microwave-medium ceramics in the low-loss of Ti base as claimed in claim 1, is characterized in that the method comprises the following steps:
1) by copper, cobalt, niobium and titanyl compound according to (1+0.7x) TiO 2-(1-x) CoO-0.1xNb 2o 5mix after the molar ratio weighing of-0.1xCuO, wherein 0.8≤x≤0.9, then abundant ball milling, ball milling post-drying, sieve and be pressed into blocks, then at 1150 DEG C, be incubated 4.5h, obtain sample and burn block;
2) by above-mentioned steps 1) sample that obtains burns block and pulverizes, then abundant ball milling, ball milling post-drying, granulation, sieves, by the particle compression moulding after sieving, then at 1200 DEG C ~ 1320 DEG C, sinter 2h become porcelain, obtain K value microwave-medium ceramics in the low-loss of Ti base.
3. the preparation method of K value microwave-medium ceramics in Ti base according to claim 2 low-loss, is characterized in that: described copper, cobalt, niobium and titanyl compound are respectively CuO, Co 2o 3, Nb 2o 5, and TiO 2.
4. the preparation method of K value microwave-medium ceramics in Ti base according to claim 2 low-loss, is characterized in that: in described step 1) and step 2) ball milling operation in, Ball-milling Time is 4h ~ 5h.
5. the preparation method of K value microwave-medium ceramics in Ti base according to claim 2 low-loss, is characterized in that: in described step 1) and step 2) baking operation in, bake out temperature is 100 ~ 120 DEG C.
6. the preparation method of K value microwave-medium ceramics in Ti base according to claim 2 low-loss, is characterized in that: in described step 1) sieve in operation, adopt 120 object screen clothes; In described step 2) sieve in operation, adopt bilayer to sieve technique, cross 60 orders and 120 object screen clothes respectively.
7. the preparation method of K value microwave-medium ceramics in Ti base according to claim 2 low-loss, is characterized in that: in described step 2) in, described granulation refers to the aqueous solution by powder and polyvinyl alcohol, then makes micron-sized spheroidal particle.
8. the preparation method of K value microwave-medium ceramics in Ti base according to claim 2 low-loss, is characterized in that: in described step 2) in, described sintering is the sintering under air atmosphere.
9. the preparation method of K value microwave-medium ceramics in Ti base according to claim 2 low-loss, is characterized in that: in described step 2) in, described compression moulding be pressed into block or cylindric.
CN201510772208.XA 2015-11-12 2015-11-12 K value microwave-medium ceramics and preparation method thereof in Ti base low-losses Active CN105314976B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510772208.XA CN105314976B (en) 2015-11-12 2015-11-12 K value microwave-medium ceramics and preparation method thereof in Ti base low-losses

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510772208.XA CN105314976B (en) 2015-11-12 2015-11-12 K value microwave-medium ceramics and preparation method thereof in Ti base low-losses

Publications (2)

Publication Number Publication Date
CN105314976A true CN105314976A (en) 2016-02-10
CN105314976B CN105314976B (en) 2017-10-31

Family

ID=55243391

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510772208.XA Active CN105314976B (en) 2015-11-12 2015-11-12 K value microwave-medium ceramics and preparation method thereof in Ti base low-losses

Country Status (1)

Country Link
CN (1) CN105314976B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109133914A (en) * 2018-11-23 2019-01-04 陕西师范大学 A kind of titanium dioxide base ceramic material of high thermal stability and preparation method thereof
CN109415265A (en) * 2017-12-25 2019-03-01 深圳市大富科技股份有限公司 A kind of medium ceramic material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004091266A (en) * 2002-08-30 2004-03-25 Daiken Kagaku Kogyo Kk Gallium-added dielectric porcelain composition, dielectric resonator, and microwave communication apparatus
CN101186496A (en) * 2007-11-27 2008-05-28 西安交通大学 Low-temperature sintering Ti-base microwave medium ceramic material and preparation thereof
CN102815944A (en) * 2012-08-27 2012-12-12 天津大学 Cobalt doped niobium zinc titanate microwave dielectric ceramics and preparation method thereof
CN104261833A (en) * 2014-09-19 2015-01-07 武汉凡谷陶瓷材料有限公司 Mediated high-Q microwave medium material for mobile communication and preparation method of mediated high-Q microwave medium material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004091266A (en) * 2002-08-30 2004-03-25 Daiken Kagaku Kogyo Kk Gallium-added dielectric porcelain composition, dielectric resonator, and microwave communication apparatus
CN101186496A (en) * 2007-11-27 2008-05-28 西安交通大学 Low-temperature sintering Ti-base microwave medium ceramic material and preparation thereof
CN102815944A (en) * 2012-08-27 2012-12-12 天津大学 Cobalt doped niobium zinc titanate microwave dielectric ceramics and preparation method thereof
CN104261833A (en) * 2014-09-19 2015-01-07 武汉凡谷陶瓷材料有限公司 Mediated high-Q microwave medium material for mobile communication and preparation method of mediated high-Q microwave medium material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUN ZHANG等: "Low temperature sintering and microwave dielectric properties of CoTiNb2O8 ceramics with CuO addition", 《CERAMICS INTERNATIONAL》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109415265A (en) * 2017-12-25 2019-03-01 深圳市大富科技股份有限公司 A kind of medium ceramic material and preparation method thereof
CN109415265B (en) * 2017-12-25 2021-09-14 大富科技(安徽)股份有限公司 Dielectric ceramic material and preparation method thereof
CN109133914A (en) * 2018-11-23 2019-01-04 陕西师范大学 A kind of titanium dioxide base ceramic material of high thermal stability and preparation method thereof
CN109133914B (en) * 2018-11-23 2021-07-06 陕西师范大学 Titanium dioxide-based ceramic material with high thermal stability and preparation method thereof

Also Published As

Publication number Publication date
CN105314976B (en) 2017-10-31

Similar Documents

Publication Publication Date Title
CN103172376B (en) Scheelite type microwave dielectric ceramic material and preparation method thereof
CN100591641C (en) Low-temperature sintering Ti-base microwave medium ceramic material and preparation thereof
CN101318815B (en) Bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature and manufacture of the same
CN101823880B (en) Phenacite type molybdenum-based and tungsten-based ultralow temperature sintered microwave dielectric ceramic materials and preparation method thereof
CN103232235B (en) Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof
CN110282968A (en) A kind of microwave dielectric ceramic materials and preparation method thereof
CN102718473B (en) Bismuth-base microwave dielectric ceramic sintered at low temperature and preparation method thereof
CN103864414A (en) Low-dielectric-constant microwave dielectric ceramic and preparation method thereof
CN101362647A (en) Low temperature sintering lithium-base microwave dielectric ceramic material and preparation thereof
CN101823879B (en) Scheelite type molybdenum-based ultralow temperature-sintered microwave dielectric ceramic material and preparation method thereof
CN103951425B (en) A kind of temperature-stable scheelite-type structure microwave-medium ceramics and preparation method thereof
CN104016670B (en) A kind of low-temperature sintering temperature-stabilized microwave medium ceramic material and preparation method thereof
CN103408299B (en) Zinc barium titanate system ceramic low temperature sintering material and preparation method thereof
CN104177085A (en) Molybdenum-based temperature-stable microwave medium ceramic and preparation method thereof
CN103467084B (en) A kind of high-k series of lithium, niobium and titanium low-temperature sintered ceramics and preparation method thereof
CN105314976A (en) Ti-based low loss K value microwave dielectric ceramic and preparation method thereof
CN104744041A (en) Temperature stable type microwave dielectric ceramic Li2Cu2Nb8O23 with low dielectric constant
JPH1072258A (en) Dielectric ceramic composition
CN103396099B (en) Niobium-based temperature-stable LTCC microwave medium ceramic material
CN102219501A (en) Lithium-based low-loss temperature-stabilized microwave medium ceramic material and preparation method thereof
CN105294103B (en) A kind of vanadium base temperature-stable microwave-medium ceramics and preparation method thereof
CN106587991B (en) Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof
CN101265097B (en) Low-temperature sintering composite microwave medium ceramic and preparation method thereof
CN104003719A (en) Microwave dielectric ceramic LiTi2V3O12 capable of being sintered at low temperature and preparation method thereof
CN104003721A (en) Microwave dielectric ceramic Li2W2Zn3O10 capable of being sintered at low temperature 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
GR01 Patent grant
GR01 Patent grant