CN1073636C - Aluminium-bath self-overgrowth reaction process - Google Patents
Aluminium-bath self-overgrowth reaction process Download PDFInfo
- Publication number
- CN1073636C CN1073636C CN98112425A CN98112425A CN1073636C CN 1073636 C CN1073636 C CN 1073636C CN 98112425 A CN98112425 A CN 98112425A CN 98112425 A CN98112425 A CN 98112425A CN 1073636 C CN1073636 C CN 1073636C
- Authority
- CN
- China
- Prior art keywords
- reaction
- aluminum
- powder
- melt
- graphite
- 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.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The present invention relates to a method for preparing a particle reinforced aluminium-based composite material, which is characterized in that the melt of aluminium or an aluminium alloy is utilized as a heat source and a protective medium, and synthesized by self-propagating reaction into reinforced phase particles or formed into coatings on the surfaces of the reinforced phase particles so as to prepare the aluminium-based composite material with the reinforced phases of SiC, graphite, TiC, TiB2, etc. The present invention enlarges the varieties of reinforced phases, enables the prepared material to have good performance, simplifies the preparation process and relevant equipment thereof, and reduces production cost.
Description
The present invention relates to a method for preparing a particle-reinforced aluminum matrix composite.
The preparation process of the particle reinforced aluminum matrix composite material is various, and the processes can be roughly divided into two types according to whether reinforcing phase particles are added from the outside or generated in the matrix: one is forced external addition; the other is an in situ reaction complex process.
So-called forced external addition, i.e. the particles of the reinforcing phase are added to the matrix from the outside. The processes commonly adopted in the prior methods mainly comprise: powder metallurgy, spray deposition, stir casting, and the like.
The powder metallurgy method and the spray deposition method have complicated preparation processes and high cost, and represent extremely high cost barriers even in the fields of aerospace and national defense with high performance requirements.
The stir casting method, i.e. the method of dispersing reinforcing phase particles into an aluminum alloy melt by means of strong mechanical stirring action, is relatively low in cost. Since the reinforcing phase particles tend to be non-wetting to the aluminum alloy melt, external forces must be applied to overcome thermodynamic surface obstacles and viscous drag to disperse the particles in the melt. The commercial production of aluminum matrix composites is achieved by the use of vacuum agitation techniques by Dural, but the difficulty of handling is increased by the use of complicated mechanical agitation devices and vacuum techniques (see us patent4,786,467). The method has great limitation on the size and volume fraction of the reinforced phase particles, the particle diameter is generally more than 10 mu m, the volume fraction is less than 40 percent, and the particles are easy to generate specific gravity segregation in a melt and form dendrite segregation during solidification to cause uneven distribution of the particles.
The coating method is to form a layer of coating which is wetted with the aluminum alloy on the surface of the reinforced phase particles through certain processes, thereby improving the wettability of the reinforced phase particles and the metal melt. For example, a Cu and Ni coating is formed on the surface of graphite or SiC particles by an electroless plating method, and then the reinforcing phase particles such as graphite and SiC, the surface of which is coated with the coating, are dispersed into an aluminum alloy melt by a mechanical stirring effect. However, this method adds a coating process, significantly increases costs, and results inThe Cu coating is easy to oxidize and melt at high temperature, the oxidized or melted coating cannot improve the wettability of particles and aluminum alloy melt, and the chemical plating Ni coating is easy to react with aluminum to generate NiAl3And the brittle phase is reduced, so that the performance of the composite material is reduced.
Compared with forced addition method, the said method has the advantages of ① reinforcing phase generated inside the matrix, clean surface and no pollutant, ② reinforcing phase and matrix interface being clean and well combined, ③ reinforcing phase generated in situ having fine particles and uniform distribution, and ④ reinforcing phase adding amount being adjustable in a large range.
The technology for preparing the particle reinforced aluminum-based composite material by the in-situ reaction composite method mainly comprises a VLS technology proposed by Koczak et al (see M.J.Koczak, M.K.PremkumarJOM.January 199344-48); SHS technology (see L.Gotman, M.J.Koczak, E.Shtessel; Mater.Sci.Eng.; A187(1994) 189-119) and XD technology (see Tao Chun Hu, Zhang Sha Qing et al, materials engineering, 1994, 11, 10-12) from Martin corporation.
The principle of the VLS technology is that inert gas containing carbon or/and nitrogen is introduced into high-temperature aluminum alloy melt, and carbon or/and nitrogen generated by gas decomposition and Ti in the alloy undergo a rapid chemical reaction to synthesize fine TiC or/and TiN particles. However, this method requires inert gas as a carrier, and since the reaction heat of the synthesis reaction is not utilized, the temperature of the aluminum alloy melt must be high to decompose the gas and perform the synthesis reaction. In addition, the kind of the reinforced phase particles is limited, and at present, only the aluminum matrix composite material taking TiC, TiN and the like as the reinforced phase can be prepared.
The SHS technology is to mix and compact various powders required by the formed product in proportion, place the compact in inert atmosphere, and ignite to make it self-propagating reaction, thereby synthesizing the composite material. The method has been used for preparing TiC and TiB2An aluminum matrix composite material as a reinforcing phase. The reaction process of the method needs to be carried out under the protection of inert atmosphere, the prepared material has more pores and needs to be processed subsequently, the preparation cost of the material is improved, when the content of the reinforcing phase is lower,the synthesis cannot be reacted, which undoubtedly increases the difficulty of the process operation. In addition, this method cannot prepare an aluminum matrix composite material using graphite, SiC, or the like as a reinforcing phase.
The XD technology is a development of the SHS technology, in which the powders required for the formation of the product are mixed in proportions and compacted, and the mixture compact is then heated in an inert atmosphere at a heating rate such that the reaction occurs spontaneously and everywhere throughout the mixture, thereby synthesizing the reinforcing phase particles. The XD technology differs from the SHS technology in the way the reaction proceeds. The SHS technique, in which the reaction process is carried out successively, relies on the propagation of a combustion wave, whereas the XD technique, in which the reaction takes place essentially simultaneously throughout the mixture. Due to the simultaneous evolution of the heat of reaction, XD technology is generally able to reach higher adiabatic temperatures than SHS technology. The method solves the problem that a system cannot be maintained because the intermetallic reaction heat release is low when an SHS technology is adopted, but cannot solve the problems that an inert atmosphere is required for protection, the prepared material contains pores and is required to be processed in a subsequent process and the like in the SHS technology. It is also impossible to prepare aluminum matrix composites with graphite, SiCp, etc. as reinforcing phases.
Chenziyong et al of Harbin university of industry propose a direct reaction synthesis process of melt, i.e. adding TiO into aluminum or aluminum alloy melt2And flux mixture, preparation A13Ti/Al composite material, or adding TiO2、KBF4Preparation of TiB with flux mixture2An aluminum composite material. However, the method has the following disadvantages: because oxides and salts are used as reaction raw materials, the reaction process is very complex and difficult to control; volatilization of low melting point salt deteriorates the operating environment; the reaction is carried out at the interface of the slag layer and the aluminum melt, the reaction speed is limited, and the operation difficulty is increased.
The invention aims to provide a preparation process of an aluminum-based composite material, which not only enlarges the variety of reinforced phases, but also simplifies the preparation process and related equipment and reduces the production cost.
In order to achieve the purpose, the invention adopts the technical scheme that: the SiC and stone are prepared by using aluminum or aluminum alloy melt as heat source and protective medium to produce self-propagating reaction to synthesize reinforced phase particles or form coating on the surface of the reinforced phase particlesInk, TiC, TiB2The aluminum matrix composite material is a reinforcing phase, and the method comprises the following steps:
① self-propagating reaction synthesis of aluminum bath, melting aluminum or aluminum alloy, overheating to 750-1050 deg.C, and mixing Ti powder and B powder4Mixing the C powder and the aluminum powder uniformly according to the weight ratio of 3: 1 to (2-4) or mixing the Ti powder, the graphite powder and the Al powder uniformly according to the weight ratio of 4: 1 to (2-3) and pressing into a green compact; pressing the pressed compact into the melt, heating the outer layer of the pressed compact to the melt temperature after 1-2 minutes to initiate synthesis reaction, and synthesizing TiB in situ2TiC reinforcing particles; the temperature of the pressed compact is further raised by the heat generated by the reaction, so that the reaction is continuously maintained until the whole pressed compact is reacted; the aluminum powder in the pressed compact is used as a diluent, so that the reaction is easy to control, the phenomenon that the pressed compact is burst to break due to the excessively violent reaction is avoided, and the addition of the aluminum powder is favorable for the dispersion of reaction products; after the reaction is finished, slightly stirring, dispersing the reaction product into the melt, and then casting to obtain TiC and TiB2An aluminum matrix composite as a reinforcing phase; by changing the addition amount of the briquettes, the volume fraction of the reinforcing phase in the composite material can be adjusted.
② aluminum bath self-propagating reaction coating is prepared through melting aluminum or aluminum alloy, overheating to 750-1050 deg.C, mixing Ti powder and graphite powder in weight ratio of 0.3-1 to 2, pressing into compact, or mixing Ti powder and SiC powder in weight ratio of 0.3-1 to 2, pressing into compact, adding the compact into the melt, heating the compact to the melt temperature for 1-2 min, and raising the temperature of the compact to maintain the reaction until the compact reacts.
The invention has the following remarkable advantages compared with the prior method because the self-propagating reaction is generated in the aluminum alloy melt, so that the enhanced phase particles or the coating on the surface of the enhanced phase particles are generated in the melt:
① the self-propagating reaction takes place in the closed aluminium melt by using the aluminium melt as heat source and protective medium, avoiding the ignition device and protective atmosphere required by the common self-propagating reaction.
② the content of the reinforcing phase can be adjusted in a larger range by changing the adding amount of the pressed compact, and the problem that the common self-propagating reaction method can only prepare the composite material with high content of the reinforcing phase is solved.
③ the components and proportion of the powder in the pressed compact are adjusted to realize the in-situ formation of the coating on the surface of the graphite or SiC reinforced phase particles, thereby simplifying and effectively preparing the coating, and the particles which can not be synthesized in situ by adopting XD technology and SHS technology can be easily and uniformly dispersed in the aluminum alloy melt.
④ because the reinforced phase particles or coating generated in situ by the self-propagating reaction has good wettability with the metal melt, the reinforced phase particles can be dispersed in the melt by low-speed stirring in the air, the complex vacuum stirring device and inert gas protection system adopted in the stirring casting method are avoided, the process is simple, and the material preparation cost is low.
⑤ the reinforcing phase particles generated in situ or the coating on the surface of the reinforcing phase particles are well combined with the interface of the matrix, and the prepared material has excellent performance.
The present invention will be described in further detail with reference to examples.
Example (b):
aluminum bath self-propagating reaction synthesis:
① mixing Ti powder and B with particle size of 20 μm4The C powder and the Al powder are evenly mixed according to the weight ratio of 3: 1: 3 and pressed into a briquetting, and the briquetting is pressed into the aluminum melt which is overheated to 850-950 ℃. After 1 minute, the briquette undergoes a self-propagating reaction according to the reaction formula In situ generating TiC and TiB2And (4) a reinforcing phase. After the reaction is finished, stirring to disperse the reaction product, and then casting and forming. And the particles are uniformly distributed on the fracture of the casting. By changing the adding amount of the pressing blocks, TiC and TiB with volume fractions of 4 percent and 10 percent are prepared respectively2The particles reinforce the Al composite material.
② mixing Ti powder and 20 μmB4C powder and lead powder are evenly mixed according to the weight ratio of 3: 1: 4 and pressed into a briquetting, and the briquetting is pressed into Al-Cu or Al-Si which is overheated to 850-950 DEG CIn the alloy melt. After 1 minute, the briquette has self-propagating reaction to form TiC and TiB in situ2And (4) reinforcing phase, after the reaction is finished, stirring to disperse the product, and then casting and forming. And the particles are uniformly distributed on the fracture of the casting. By changing the adding amount of the pressing blocks, TiC and TiB with the volume content of 4 percent and 10 percent are prepared2A composite material for reinforcing an aluminum alloy matrix.
③ Ti powder, graphite powder and 20-30 μm aluminum powder are mixed uniformly according to the weight ratio of 4: 1: 3 and pressed into a briquetting, the briquetting is pressed into an aluminum melt at 850-950 ℃ for 1 minute, the briquetting is initiated by the aluminum melt to carry out self-propagating reaction, TiC particles are generated in situ, after the reaction is finished, the briquetting is stirred to disperse, and casting forming is carried out, from the fracture of a casting, the particles are distributed uniformly, and the TiC/aluminum composite material with the TiC volume fraction of 4% and 10% is prepared by changing the adding amount of the briquetting.
④ Ti powder, graphite powder and aluminium powder are mixed uniformly according to the weight ratio of 4: 1: 2 and pressed into a briquetting, the briquetting is pressed into Al-Cu or Al-Si alloy melt which is overheated to 850-950 ℃, after 1 minute, the briquetting carries out self-propagating reaction, TiC particles are generated in situ in the aluminum alloy melt, after the reaction is finished, the briquetting is stirred to be dispersed, and casting forming is carried out, from the fracture of a casting, the particles are distributed uniformly, and TiC/Al alloy composite materials with the TiC volume fractions of 4% and 10% are prepared by changing the adding quantity of the briquetting.
Self-propagating reactive coating for aluminum bath
⑤ Ti powder and 20-30 μm graphite powder are mixed uniformly according to the weight ratio of 0.5: 2, pressed into a briquetting, pressed into an aluminum melt overheated to 850-950 ℃, after 1-2 minutes, the outer layer of the briquetting reacts and then spreads to the whole briquetting, a TiC coating is formed on the surface of graphite particles, stirred by a graphite stick, the briquetting is uniformly dispersed into the melt, and cast to form, from the fracture of a casting, graphite is uniformly distributed, and by changing the adding amount of the briquetting, a Grp/Al composite material with the graphite volume fractions of 4%, 8% and 12% is prepared.
⑥ Ti powder and 20-30 μm graphite powder are mixed uniformly according to the weight ratio of 1: 2, pressed into a briquetting, pressed into an Al-Si or Al-Cu melt which is overheated to 750-850 ℃, and subjected to self-propagating reaction for 1-2 minutes to form a TiC coating on the surface of graphite particles in situ, stirred with graphite sticks, and cast to form the graphite composite material with graphite volume fractions of 4%, 8% and 12% by changing the adding amount of the briquetting.
⑦ Ti powder and 14-20 mu m SiC powder are mixed evenly according to the weight ratio of 0.5: 2 and pressed into a briquetting, the briquetting is pressed into an aluminum melt which is overheated to 950-1050 ℃, the outer layer of the briquetting reacts after 1-2 minutes and then spreads to the whole briquetting, a coating is generated on the surface of SiC particles in situ, the briquetting is dispersed into the melt by stirring, and casting forming is carried out, SiC is distributed evenly from the fracture of a casting, and the SiC/Al composite material with SiC volume fractions of 4%, 8%, 12% and 20% is prepared by changing the adding amount of the briquetting.
⑧, evenly mixing Ti powder and 14-20 mu m SiC powder according to the weight ratio of 1: 2, pressing into a briquetting, pressing the briquetting into an Al-Si or Al-Cu melt overheated to 850-950 ℃, after 1-2 minutes, the briquetting has a self-propagating reaction, and a coating is generated on the surface of SiC particles in situ, stirring to disperse the SiC particles into the melt, and casting to form, wherein the SiC is evenly distributed from the fracture of a casting to prepare the SiC/Al alloy composite material with SiC volume fractions of 4%, 8%, 12% and 20%.
Claims (2)
1. The method for preparing the particle reinforced aluminum matrix composite material by the aluminum bath self-propagating reaction is characterized by comprising the following steps of: SiC, graphite, TiC and TiB are prepared by using aluminum or aluminum alloy melt as heat source and protective medium and producing self-propagating reaction to synthesize enhanced phase particles2Aluminum matrix composite materials with equal reinforcing phase: firstly, melting and overheating aluminum or aluminum alloy to 750-1050 ℃, and then, adding Ti powder and B powder4Mixing the C powder and the aluminum powder uniformly according to the weight ratio of 3: 1 to (3-4) or mixing the Ti powder, the graphite powder and the Al powder uniformly according to the weight ratio of 4: 1 to (2-3), pressing the mixture into a pressed blank, and pressing the pressed blank into the melt. After 1-2 minutes, the outer layer of the pressed compact is heated to the temperature of the melt to initiate a synthesis reaction, and the temperature of the pressed compact is further raised by reaction heat generated by the reaction to continuously maintain the reaction until the whole pressed compact is reacted; the aluminum powder in the green compact is used as a diluent, so that the reaction is easy to control, and the dispersion of reaction products is facilitated; slightly stirring to disperse the reaction product into the melt; then casting to obtain TiC and TiB2An aluminum matrix composite as a reinforcing phase; the volume fraction of the reinforcing phase in the composite material is adjusted by varying the amount of green compact added.
2. The method for preparing the particle reinforced aluminum matrix composite material by the aluminum bath self-propagating reaction is characterized by comprising the following steps of: the SiC, graphite, TiC and TiB are prepared by using aluminum or aluminum alloy melt as heat source and protective medium and generating self-propagating reaction to generate a coating on the surface of reinforced phase particles2Aluminum matrix composite materials with equal reinforcing phase: firstly, melting aluminum or aluminum alloy, overheating to 750-1050 ℃, then mixing Ti powder and graphite powder according to the weight ratio of (0.5-1) to 2 and pressing into a green compact, or mixing Ti powder and SiC powder according to the weight ratio of (0.5-1) to 2 and pressing into a green compact, and then adding the green compact into a melt. After 1-2 minutes, the outer layer of the pressed compact is heated to the temperature of the melt to initiate a synthesis reaction, and the temperature of the pressed compact is further raised by reaction heat generated by the reaction to continuously maintain the reaction until the whole pressed compact is reacted;since the graphite or SiC in the compact is in excess and the amount of Ti is small, only the graphite or SiC surface layer is consumed, and thus in these reinforcing phasesA coating is formed on the surface, excessive graphite and SiC play a role in diluting like aluminum powder, so that the reaction process is carried out stably; slightly stirring to uniformly disperse the reacted particles into the melt, and then casting to prepare the graphite or SiC particle reinforced aluminum matrix composite material containing the coating; the adding amount of the briquettes is changed, and the volume fraction of the reinforcing phase in the composite material is adjusted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112425A CN1073636C (en) | 1998-04-09 | 1998-04-09 | Aluminium-bath self-overgrowth reaction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112425A CN1073636C (en) | 1998-04-09 | 1998-04-09 | Aluminium-bath self-overgrowth reaction process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231342A CN1231342A (en) | 1999-10-13 |
| CN1073636C true CN1073636C (en) | 2001-10-24 |
Family
ID=5222277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98112425A Expired - Fee Related CN1073636C (en) | 1998-04-09 | 1998-04-09 | Aluminium-bath self-overgrowth reaction process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1073636C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376705C (en) * | 2002-12-11 | 2008-03-26 | 山东大学 | Prepn of alumina-titanium carbide particle reinforced aluminium-base composite material |
| CN100422368C (en) * | 2004-07-05 | 2008-10-01 | 北京有色金属研究总院 | In situ formed TiC reinforced Al-Fe-V-Si series heat resistant aluminium alloy material and its preparation method |
| CN101748306B (en) * | 2008-12-02 | 2011-12-07 | 苏州有色金属研究院有限公司 | Multiphase ceramic hybrid composite reinforced metal matrix composite material and preparation process thereof |
| CN102623079A (en) * | 2012-03-31 | 2012-08-01 | 西南科技大学 | High-temperature self-propagating curing method for strontium-containing radioactive graphite |
| CN104372208B (en) * | 2014-10-28 | 2019-03-29 | 赵遵成 | A kind of endogenetic particle hybrid reinforced aluminum-matrix composite material and preparation method thereof |
| CN104848186B (en) * | 2015-04-24 | 2018-07-24 | 东莞市闻誉实业有限公司 | Radiator |
| CN109972063A (en) * | 2019-04-18 | 2019-07-05 | 江苏金洋机械有限公司 | A kind of high rigidity high tenacity aluminum matrix composite and preparation method thereof |
| CN110144479B (en) * | 2019-05-15 | 2020-06-16 | 内蒙古工业大学 | Method for in-situ synthesis of aluminum-based composite material with hierarchical structure |
| CN112375935B (en) * | 2020-11-24 | 2022-03-11 | 中北大学 | Method for preparing high-temperature-resistant high-strength cast aluminum-copper alloy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031115A (en) * | 1987-07-15 | 1989-02-15 | 兰克西敦技术公司 | Prepare the method for self-supporting body and the product of manufacturing thereof |
-
1998
- 1998-04-09 CN CN98112425A patent/CN1073636C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031115A (en) * | 1987-07-15 | 1989-02-15 | 兰克西敦技术公司 | Prepare the method for self-supporting body and the product of manufacturing thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1231342A (en) | 1999-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Panwar et al. | Fabrication methods of particulate reinforced Aluminium metal matrix composite-A review | |
| Wang et al. | Fabrication of TiB2 and TiB2–TiC particulates reinforced magnesium matrix composites | |
| CN1081675C (en) | TiB2 particulate ceramic reinforced Al-alloy metal-matrix composites | |
| KR950014105B1 (en) | Process for forming metal-second phase composites and product thereof | |
| CN111206166B (en) | Preparation method of in-situ ternary nanoparticle reinforced aluminum matrix composite | |
| CN112048629A (en) | Preparation method of Al-Ti-Nb-B refiner for casting aluminum-silicon alloy | |
| CN1073636C (en) | Aluminium-bath self-overgrowth reaction process | |
| CN112593111B (en) | Carbide nanoparticle modified aluminum-based nanocomposite and preparation method thereof | |
| EP2514542B1 (en) | Production method and production device for a composite metal powder using the gas spraying method | |
| CN102791893B (en) | Particulate aluminium matrix nano-composites and a process for producing the same | |
| CN112281014A (en) | Preparation method of rare earth alloyed magnesium-lithium alloy or aluminum-lithium alloy | |
| Jiang et al. | Fabrication of TiCp/Mg composites by the thermal explosion synthesis reaction in molten magnesium | |
| CN114672686B (en) | Preparation method of additional nano-particle reinforced cast aluminum-lithium alloy | |
| CN107974569A (en) | A kind of preparation method of aluminium based composite material enhanced by miscellaneous granules | |
| CN103695673B (en) | A kind of intermetallic compound particle Al 3the preparation method of-M reinforced aluminum matrix composites | |
| CN1152969C (en) | Process for preparing particle reinforced Mg-base composite | |
| RU2567779C1 (en) | Method of producing of modified aluminium alloys | |
| CN1226438C (en) | Method for preparing aluminium base alloy of containing T10 and AL2O3 particles | |
| CN1727506A (en) | Method for preparing aluminium based composite material enhanced by miscellaneous granules in situ | |
| CN110004316B (en) | Preparation method of in-situ nano ceramic particle reinforced aluminum-based composite material | |
| CN112853175B (en) | Preparation method of high-strength and high-toughness aluminum alloy section based on nano in-situ/precipitated phase regulation mechanism | |
| CN112662909B (en) | Carbide nanoparticle modified die-casting aluminum alloy and preparation method thereof | |
| CN112522533B (en) | Method for preparing in-situ nanoparticle reinforced aluminum matrix composite at low temperature | |
| CN1417362A (en) | Prepn of alumina-titanium carbide particle reinforced aluminium-base composite material | |
| CN1317407C (en) | Method for producing steel bonded carbide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |