CN101704313B - Structural high-damping fiber-reinforced composite - Google Patents

Structural high-damping fiber-reinforced composite Download PDF

Info

Publication number
CN101704313B
CN101704313B CN2009101723420A CN200910172342A CN101704313B CN 101704313 B CN101704313 B CN 101704313B CN 2009101723420 A CN2009101723420 A CN 2009101723420A CN 200910172342 A CN200910172342 A CN 200910172342A CN 101704313 B CN101704313 B CN 101704313B
Authority
CN
China
Prior art keywords
composite
damping
flexible
material layer
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2009101723420A
Other languages
Chinese (zh)
Other versions
CN101704313A (en
Inventor
郭万涛
冀冰
吴医博
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.)
725th Research Institute of CSIC
Original Assignee
725th Research Institute of CSIC
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 725th Research Institute of CSIC filed Critical 725th Research Institute of CSIC
Priority to CN2009101723420A priority Critical patent/CN101704313B/en
Publication of CN101704313A publication Critical patent/CN101704313A/en
Application granted granted Critical
Publication of CN101704313B publication Critical patent/CN101704313B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention discloses a structural high-damping fiber-reinforced composite, which comprises a flexible damping composite intermediate layer and a rigid composite outer layer, wherein both the flexible damping composite intermediate layer and the rigid composite outer layer are plain, satin and cross grain fabrics which are combined by resin matrixes and reinforced fibers that are basalt fibers or high-strength or high-modulus glass fibers; the resin matrix of the intermediate layer is a mixture of flexible epoxy resin and common flexible epoxy resin in a certain proportion and the resin matrix of the outer layer is common epoxy resin; and the epoxy value of the flexible epoxy resin is 0.2 to 0.4 and is reinforced and modified by a rubber elastomer, thermoplastic resin, organic silicon and a thermotropic liquid crystalline polymer. The composite has the advantages that: the drawback brought by damping modification of resin that the mechanical performance of the damping composite degrades obviously is overcome and the loss factor in damping of the composite is more than 0.05 on the basis of retaining the mechanical performance of the common fiber reinforced composite; and the performance-to-price ratio of the raw material is high, and application range of the structural high-damping fiber-reinforced composite is enlarged.

Description

A kind of structural high-damping fiber-reinforced composite
Technical field
The present invention relates to a kind of nonmetallic composite technology, particularly a kind of structural high-damping fiber-reinforced composite.
Background technology
The structural type damp composite material is a kind of fiber-resin composite that has excellent damping performance and certain mechanical property concurrently, and means such as the damping coating of main damping modification through resin matrix, fiber surface, the design of fiber lay down layer realize the structure-function integration of material.
European patent EP 0337443 A1 discloses a kind of damp composite material; The damping capacity that should be used for improving composite through the damping modification resin; Its resin matrix adopts xylylene amine and position, α end straight chain binary aliphatic ester to synthesize; Be called for short " MX nylon ", reinforcing material adopts glass fibre.The damp composite material that adopts said method to make has reasonable damping capacity, but mechanical properties decrease is very serious, can't use as structural material.The domestic scholar of having adopts carboxylic acrylonitrile butadiene rubber modified epoxy to improve the composite damping capacity, adds the XNBR of 18% (weight), and composite damping capacity (fissipation factor) doubles, but intensity receives greater loss.
In fortifying fibre surface-coated damping coating, utilize the big detrusion dissipates vibration energy of high damping interface transition layer, can significantly improve the damping capacity of composite.People such as Wuhan Polytechnical Univ Wen Di river adopt the composite of the glass fibre preparation of the titanate esters processing with soft segment to compare damping capacity with the composite that common process liquid is handled has significantly raising.Adopt the weak point of this raising composite damping capacity approach to be: composite is when damping capacity improves, and its mechanical property (especially interlaminar shear strength and bending modulus) descends significantly.
Fiber lay down layer design also is to improve composite damping capacity a kind of technological approaches commonly used in addition, through fiber lay down layer angle and optimization or mix the shop layer and design the damping capacity that improves composite.Method relatively more commonly used mixes for adopting good kevlar fiber of damping capacity and excellent graphite fibre or the high-performance glass fiber of mechanical property; Adopt the kevlar fiber lay down to overlay on material outer layer; Graphite fibre or high-performance glass fiber shop overlay on the sandwich promiscuous mode of internal layer, and the damping capacity of material is doubled, and the problem of its existence is: although composite still keeps better mechanical property; But the damping capacity of material is not high enough; Be generally 0.01~0.03, cost is too high in addition, is unfavorable for applying of material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of structural high-damping fiber-reinforced composite; Utilize the reasonable combination of rigid composite material layer and flexible damp composite material layer, obtain a kind of fiber-resin composite that has excellent damping performance and certain mechanical property cheaply concurrently.
For the purpose that realizes solving the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of structural high-damping fiber-reinforced composite of the present invention; Comprise intermediate layer of material, material outer layer; Intermediate layer of material is flexible damp composite material layer; Material outer layer adopts the rigid composite material layer, and intermediate layer of material and material outer layer material are the composite of fortifying fibre and resin matrix composition, and fortifying fibre adopts basalt fibre, high-strength or high mould glass fibre; The resin matrix of flexible damp composite material layer adopts the complex of flexible-epoxy and ordinary epoxy resin, and rigid composite material layer resin matrix adopts ordinary epoxy resin; Said flexible-epoxy epoxide number 0.2~0.4; Be with the epoxy resin after rubber elastomer, thermoplastic resin, organosilicon or the thermotropic liquid crystal polymer toughening modification; Commercially available common product has 6350 of LG-DOW DER732, homemade Shanghai Resin Factory, and the LER0350 of hundred million companies etc. is managed in Shanghai; Described flexible-epoxy and ordinary epoxy resin complex by a certain percentage; Its prescription is 20~80 parts of ordinary epoxy resins, 20~80 parts of flexible-epoxies, 10~20 parts in T31 curing agent; 15~40 parts in 5784 curing agent; 0.5~3 part of KH560 coupling agent, 1~3 part of the white carbon black of gas phase, 5~10 parts of 501 diluents; Resin matrix formulation weight part of described rigid composite material layer consists of: 100 parts of ordinary epoxy resins, 15~40 parts in T31 curing agent 10~20,5784 curing agent, 0.5~3 part of KH560 coupling agent, 1~3 part of the white carbon black of gas phase, 5~10 parts of 501 diluents.The cost performance of flexible damping layer and basalt fibre that rigid layer uses, high-strength or high mould glass fibre is higher, and flexible damping layer and rigid layer resin matrix adopt the resin matrix of close type to guarantee the adhesive strength between two-layer.
Flexible-epoxy of the present invention and ordinary epoxy resin complex by a certain percentage, its condition of cure can ordinary epoxy resin condition of cure, also can be normal temperature cure 24 hours, solidified 6 hours after 80 ℃.Employed product among the present invention; Do not indicate the commercially available common product of being of producer; The trade mark is the general trade mark, and like E51 epoxy resin, E44 epoxy resin, curing agent T31, curing agent 5784, curing agent 5506, diluent 501 can be bought in Shanghai Resin Factory; The KH560 coupling agent can dawn coupling agent company be bought in Nanjing, and the white carbon black of gas phase can chemical industry joint-stock company be bought in Shenyang; The said goods also can select for use other producers to have the product of similar structures.
A kind of structural high-damping fiber-reinforced composite of the present invention; Its concrete technical scheme can be: the reinforcing material basalt fibre of described flexible damp composite material layer, high-strength or high mould glass fabric, its weaving manner can be plain weave, satin weave, twill.
A kind of structural high-damping fiber-reinforced composite of the present invention; Its concrete technical scheme can also be: described ordinary epoxy resin is the glycidol ether type epoxy; Require epoxide number 0.4~0.8, comprise the commercially available common trade mark: homemade E51, homemade E44, homemade E55, LG-DOW DER331, Japanese YD-128 and product with similar structures.
A kind of structural high-damping fiber-reinforced composite of the present invention, its concrete technical scheme can also be: the fiber content percentage by weight of described flexible damp composite material layer is 35~65%, thickness is 1~15mm.
A kind of structural high-damping fiber-reinforced composite of the present invention; Its concrete technical scheme can also be: the resin matrix condition of cure of described rigid composite material layer can use the condition of cure of ordinary epoxy resin; Comprising can normal temperature cure 24 hours, solidifies 6 hours after 80 ℃.
A kind of structural high-damping fiber-reinforced composite of the present invention; Its concrete technical scheme can also be: the reinforcing material basalt fibre of described rigid composite material layer, high-strength or high mould glass fabric, its weaving manner can be plain weave, satin weave, twill.
A kind of structural high-damping fiber-reinforced composite of the present invention, its concrete technical scheme can also be: the resin content percentage by weight of described rigid layer composite layer is 50~75%, the rigid composite material layer thickness is 0.25~7.5mm.
A kind of structural high-damping fiber-reinforced composite of the present invention, its concrete technical scheme can also be: described rigid layer composite layer is 1: 10~1: 2 with flexible damp composite material layer thickness ratio.
Technical scheme that these are concrete and optimized technical scheme also can mutual combination be used, thereby reach better technique effect.
Through adopting technique scheme; A kind of structural high-damping fiber-reinforced composite of the present invention has overcome the damp composite material mechanical properties decrease significant disadvantage that adopts the resin damping modification to be brought; On the basis that keeps general fibre reinforced composite mechanical property, the damping loss factor of material reaches more than 0.05; Used raw-material cost performance has been widened the application of structural high-damping fiber-reinforced composite than higher.
Description of drawings
Fig. 1 is a kind of structural high-damping fiber-reinforced composite schematic cross-section of the present invention, and wherein 1 is flexible damp composite material layer, and 2 is the rigid composite material layer.
The specific embodiment
Employed product in the embodiment of the invention; E51 epoxy resin, E44 epoxy resin; Curing agent T31, curing agent 5784, curing agent 5506, diluent 501 are Shanghai Resin Factory's product; The KH560 coupling agent is a Nanjing dawn coupling agent Company products, and the white carbon black of gas phase is a Shenyang chemical industry joint-stock company product.
Embodiment 1
Rigid layer composite layer 2 is 1: 8 with flexible damp composite material layer 1 thickness ratio.Each part requirement following:
Flexible damp composite material layer 1:
The reinforcing material of flexible damp composite material layer 1 adopts the basalt fibre plain; The resin matrix prescription of flexible damp composite material layer consists of (weight portion): 40 parts of E-51 epoxy resin, 60 parts of DER732 flexible-epoxies, 10 parts in T31 curing agent; 5784 curing agent 40; 1.5 parts of KH560 coupling agents, 1 part of the white carbon black of gas phase, 5 parts of 501 diluents.Condition of cure is normal temperature cure 24 hours, solidifies 6 hours after 80 ℃.
The fiber content of flexible layer composite (percentage by weight) is 65%, and flexible damp composite material layer 1 thickness is 8mm.
Rigid composite material layer 2:
The reinforcing material of rigid composite material layer 2 adopts the basalt fibre plain; The resin matrix prescription of rigid composite material layer consists of (weight portion): 100 parts of E51 epoxy resin; 40 parts in T31 curing agent 10,5784 curing agent, 0.5 part of KH560 coupling agent; 3 parts of the white carbon blacks of gas phase, 10 parts of 501 diluents.Condition of cure is normal temperature cure 24 hours, solidifies 6 hours after 80 ℃.
The resin content of rigid layer composite (percentage by weight) is 50%, and rigid composite material layer 2 thickness are 1mm.
Testing mechanical property and the damping capacity result of this composite under 23 ℃ is:
Bending strength: 391.22MPa, bending modulus: 17.17GPa;
The mean value of 0~300Hz scope internal loss factor is 0.05.
Embodiment 2:
Rigid layer composite layer 2 is 1: 2 with flexible damp composite material layer 1 thickness ratio.Each part requirement following:
Flexible damp composite material layer 1:
The reinforcing material of flexible damp composite material layer 1 adopts the high mould glass fibre of MW210 twills; The resin matrix prescription of flexible damp composite material layer consists of (weight portion): 20 parts of DER331 epoxy resin, 6350 flexible-epoxies divide 80 parts, T31 curing agent 20; 25 parts in 5784 curing agent; 1.5 parts of KH560 coupling agents, 2 parts of the white carbon blacks of gas phase, 8 parts of 501 diluents.Condition of cure is normal temperature cure 24 hours, solidifies 6 hours after 80 ℃.
The fiber content of flexible layer composite (percentage by weight) is 50%, and flexible damp composite material layer 1 thickness is 15mm.
Rigid composite material layer 2:
The reinforcing material of rigid composite material layer 2 adopts the high mould glass fibre of MW210 twills; Rigid composite material layer resin matrix prescription consists of (weight portion): 100 parts of DER331 epoxy resin; 25 parts in T31 curing agent 15,5784 curing agent, 0.5 part of KH560 coupling agent; 2 parts of the white carbon blacks of gas phase, 8 parts of 501 diluents.Condition of cure is normal temperature cure 24 hours, solidifies 6 hours after 80 ℃.
The resin content of rigid layer composite (percentage by weight) is 75%, and rigid composite material layer 2 thickness are 7.5mm.
Testing mechanical property and the damping capacity result of this composite under 23 ℃ is:
Bending strength: 446.36MPa, bending modulus: 18.33GPa;
The mean value of 0~300Hz scope internal loss factor is 0.03.
Embodiment 3:
Rigid layer composite layer 2 is 1: 4 with flexible damp composite material layer 1 thickness ratio.Each part requirement following:
Flexible damp composite material layer 1:
The reinforcing material of flexible damp composite material layer 1 adopts the high mould glass fibre of MW210 twills; The resin matrix prescription of flexible damp composite material layer consists of (weight portion): 50 parts of E44 epoxy resin, 50 parts of LER0350 flexible-epoxies, T31 curing agent 15; 40 parts in 5784 curing agent; 1.5 parts of KH560 coupling agents, 1 part of the white carbon black of gas phase, 5 parts of 501 diluents.Condition of cure is normal temperature cure 24 hours, solidifies 6 hours after 80 ℃.
The fiber content of flexible layer composite (percentage by weight) is 50%, and flexible damp composite material layer 1 thickness is 1mm.
Rigid composite material layer 2:
The reinforcing material of rigid composite material layer 2 adopts the high mould glass fibre of MW210 twills; The resin matrix prescription of rigid composite material layer 2 consists of (weight portion): 100 parts of E44 epoxy resin; 40 parts in T31 curing agent 10~20,5784 curing agent, 1.5 parts of KH560 coupling agents; 1 part of the white carbon black of gas phase, 5 parts of 501 diluents.
The resin content of rigid layer composite (percentage by weight) is 65%, and rigid composite material layer 2 thickness are 0.25mm.
Testing mechanical property and the damping capacity result of this composite under 23 ℃ is:
Bending strength: 409.99MPa, bending modulus: 18.39GPa;
The mean value of 0~300Hz scope internal loss factor is 0.04.
Comparative Examples:
A kind of homemade fibre reinforced composites, reinforcing material is selected S for use 2The satin weave high strength glass fiber sheet, the prescription of resin matrix consists of: 50 parts of E51 epoxy resin, 50 parts of DER732 epoxy resin, 30 parts in 5506 curing agent, 1 part of KH560 coupling agent, 1 part of the white carbon black of gas phase, 5 parts of 501 diluents.Condition of cure is normal temperature cure 24 hours, solidifies 6 hours after 80 ℃.
Testing mechanical property and the damping capacity result of this composite under 23 ℃ is:
Bending strength: 302.00MPa, bending modulus: 16.81GPa;
The mean value of 0~300Hz scope internal loss factor is 0.05.
In Comparative Examples, damping capacity is suitable with embodiment 1, and the mean value of 0~300Hz scope internal loss factor is 0.05, but bending modulus and bending strength descend 20%.

Claims (7)

1. structural high-damping fiber-reinforced composite; Comprise intermediate layer of material, material outer layer; It is characterized in that: intermediate layer of material is flexible damp composite material layer; Material outer layer adopts the rigid composite material layer, and intermediate layer of material and material outer layer material are the composite of fortifying fibre and resin matrix composition, and fortifying fibre adopts basalt fibre, high-strength or high mould glass fibre; The resin matrix of flexible damp composite material layer adopts the complex of flexible-epoxy and ordinary epoxy resin, and rigid composite material layer resin matrix adopts ordinary epoxy resin; Said flexible-epoxy epoxide number 0.2~0.4 is with the epoxy resin after rubber elastomer, thermoplastic resin, organosilicon or the thermotropic liquid crystal polymer toughening modification; Described flexible-epoxy and ordinary epoxy resin complex by a certain percentage; Its prescription is 20~80 parts of ordinary epoxy resins, 20~80 parts of flexible-epoxies, 10~20 parts in T31 curing agent; 15~40 parts in 5784 curing agent; 0.5~3 part of KH560 coupling agent, 1~3 part of the white carbon black of gas phase, 5~10 parts of 501 diluents; Resin matrix formulation weight part of described rigid composite material layer consists of: 100 parts of ordinary epoxy resins, 15~40 parts in T31 curing agent 10~20,5784 curing agent, 0.5~3 part of KH560 coupling agent, 1~3 part of the white carbon black of gas phase, 5~10 parts of 501 diluents.
2. according to the said a kind of structural high-damping fiber-reinforced composite of claim 1; It is characterized in that: the reinforcing material basalt fibre of described flexible damp composite material layer, high-strength or high mould glass fabric, its weaving manner is plain weave, satin weave or twill.
3. according to the said a kind of structural high-damping fiber-reinforced composite of claim 1, it is characterized in that: described ordinary epoxy resin is the glycidol ether type epoxy, epoxide number 0.4~0.8.
4. according to the said a kind of structural high-damping fiber-reinforced composite of claim 1, it is characterized in that: the fiber content percentage by weight of described flexible damp composite material layer is 35~65%, and thickness is 1~15mm.
5. according to the said a kind of structural high-damping fiber-reinforced composite of claim 1, it is characterized in that: the resin content percentage by weight of described rigid composite material layer is 50~75%, and the rigid composite material layer thickness is 0.25~7.5mm.
6. according to the said a kind of structural high-damping fiber-reinforced composite of claim 1, it is characterized in that: the reinforcing material basalt fibre of described rigid composite material layer, high-strength or high mould glass fabric, its weaving manner is plain weave, satin weave or twill.
7. according to the said a kind of structural high-damping fiber-reinforced composite of claim 1, it is characterized in that: described rigid composite material layer is 1: 10~1: 2 with flexible damp composite material layer thickness ratio.
CN2009101723420A 2009-09-22 2009-09-22 Structural high-damping fiber-reinforced composite Active CN101704313B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009101723420A CN101704313B (en) 2009-09-22 2009-09-22 Structural high-damping fiber-reinforced composite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009101723420A CN101704313B (en) 2009-09-22 2009-09-22 Structural high-damping fiber-reinforced composite

Publications (2)

Publication Number Publication Date
CN101704313A CN101704313A (en) 2010-05-12
CN101704313B true CN101704313B (en) 2012-03-14

Family

ID=42374593

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009101723420A Active CN101704313B (en) 2009-09-22 2009-09-22 Structural high-damping fiber-reinforced composite

Country Status (1)

Country Link
CN (1) CN101704313B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102179978B (en) * 2011-02-15 2013-10-02 中国船舶重工集团公司第七二五研究所 Sandwich damping composite material
CN103264555B (en) * 2013-05-20 2015-06-03 四川辉腾科技有限公司 Composite resin material capable of resisting high and low temperatures and high-energy radiation environment, and preparation method thereof
CN105542695A (en) * 2016-02-02 2016-05-04 江苏同盟汽车零部件实业有限公司 High-damping reinforcing rubber sheet and preparation method thereof
CN109262562A (en) * 2017-07-18 2019-01-25 宜兴市泰宇汽车零部件有限公司 EPP instrument cases
CN108299700A (en) * 2018-01-23 2018-07-20 嘉兴学院 A kind of Novel high-damping isolation rubber composite material, preparation method and applications
JP6980563B2 (en) * 2018-02-28 2021-12-15 日鉄ケミカル&マテリアル株式会社 Laminated material for reinforcement of structure, reinforcement method and reinforcement structure
CN109336417A (en) * 2018-08-21 2019-02-15 江苏大学 A kind of preparation method and applications of surface grafting functional polymer treated basalt fiber
CN109320919A (en) * 2018-11-09 2019-02-12 陈鹏 A kind of shock-absorbing bridge support composite material and preparation method
CN109533260B (en) * 2018-11-19 2021-05-28 中国舰船研究设计中心 Ship stern bearing restraint isolation structure device
CN111941896A (en) * 2020-07-27 2020-11-17 明阳智慧能源集团股份公司 Method for improving damping performance of wind driven generator blade
CN112064019B (en) * 2020-08-22 2022-06-14 安徽江南泵阀集团有限公司 Bearing improvement process for reducing vibration intensity of chemical pump

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101056496A (en) * 2006-02-24 2007-10-17 三洋电机株式会社 Flexible substrate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101056496A (en) * 2006-02-24 2007-10-17 三洋电机株式会社 Flexible substrate

Also Published As

Publication number Publication date
CN101704313A (en) 2010-05-12

Similar Documents

Publication Publication Date Title
CN101704313B (en) Structural high-damping fiber-reinforced composite
Li et al. Multi-scaled enhancement of damping property for carbon fiber reinforced composites
CN102179978B (en) Sandwich damping composite material
CN103727203B (en) compound gear and gear shaft
Valença et al. Evaluation of the mechanical behavior of epoxy composite reinforced with Kevlar plain fabric and glass/Kevlar hybrid fabric
Wong et al. Improved fracture toughness of carbon fibre/epoxy composite laminates using dissolvable thermoplastic fibres
CA2467135C (en) Composite material with improved damping characteristics and method of making same
Bilge et al. Global and local nanofibrous interlayer toughened composites for higher in-plane strength
CN102930862B (en) Z-direction enhanced underwater sound absorption sandwich composite material and preparation method for same
Lim et al. Effect of stacking sequence on the flexural and fracture properties of carbon/basalt/epoxy hybrid composites
CN111113946A (en) Hybrid composite laminated board and preparation process thereof
Zheng et al. Preparation and damping properties of medium-temperature co-cured phenolic resin matrix composite structures
CN111393800A (en) Epoxy resin suitable for pultrusion process and carbon fiber composite material thereof
CN103665771A (en) Wear-resistant composition, wear-resistant gear and manufacturing method of wear-resistant gear
CN102532881B (en) Acicular wollastonite powder composite material for nylon 6 modification and preparation method thereof
Pei et al. Temperature effects on structural integrity of fiber‐reinforced polymer matrix composites: A review
CN116694030A (en) Ultra-light high-strength composite material and preparation method and application thereof
Vasudevan et al. Effect of Kevlar ply orientation on mechanical characterization of Kevlar-glass fiber laminated composites
CN110804281A (en) Preparation method of graphene-reinforced carbon fiber epoxy prepreg
KR20180116511A (en) Manufacturing method of carbon fiber reinforced plastics, carbon fiber reinforced resin composite and molded article using the same
Kumar et al. Study on reinforcement materials for nylon matrix composites—a review
CN110951432A (en) Epoxy resin building structural adhesive and preparation method thereof
CN114426404A (en) Continuous basalt fiber composite rubber conveying belt and preparation method thereof
Shaari et al. Effect of hybridization on open-hole tension properties of woven Kevlar/glass fiber hybrid composite laminates
CN105419326A (en) Coupling agent treated glass fiber reinforced polyimide composite material

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