CN115679227A - High-strength toughened bolt and heat treatment process thereof - Google Patents

High-strength toughened bolt and heat treatment process thereof Download PDF

Info

Publication number
CN115679227A
CN115679227A CN202211377421.7A CN202211377421A CN115679227A CN 115679227 A CN115679227 A CN 115679227A CN 202211377421 A CN202211377421 A CN 202211377421A CN 115679227 A CN115679227 A CN 115679227A
Authority
CN
China
Prior art keywords
bolt
heat treatment
furnace
temperature
strength
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
CN202211377421.7A
Other languages
Chinese (zh)
Inventor
李贵智
陶波
范静
宫政
陈世洲
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.)
China Railway Longchang Materials Co Ltd
Original Assignee
China Railway Longchang Materials Co Ltd
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 China Railway Longchang Materials Co Ltd filed Critical China Railway Longchang Materials Co Ltd
Priority to CN202211377421.7A priority Critical patent/CN115679227A/en
Publication of CN115679227A publication Critical patent/CN115679227A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Landscapes

  • Heat Treatment Of Articles (AREA)

Abstract

The invention discloses a high-strength strengthening and toughening bolt and a heat treatment process thereof, and the process comprises the following steps: s1, pre-induction normalizing of a bolt; s2, placing the bolt in a continuous mesh belt quenching furnace, wherein the quenching temperature is 820-900 ℃, the time in the furnace is 50-60min, and the cooling medium is inorganic aqueous solution; s3, placing the bolt in a continuous mesh belt tempering furnace, wherein the tempering temperature is 500-550 ℃, the time in the furnace is 90-120min, and the cooling medium is water; s4, placing the bolt in a well type tempering furnace, heating to 500-550 ℃ from room temperature, keeping the temperature for 75-105min, and taking air as a cooling medium. After the heat treatment of the invention, the tensile strength of the bolt obtained by the invention can reach 1350MPa and impact absorption power KV at-20 DEG C 2 The performance of the bolt reaches more than 100J, the performance of the bolt is far superior to 10.9 or 12.9 grade in the standard, and no fatigue fracture failure occurs in use.

Description

High-strength strengthening and toughening bolt and heat treatment process thereof
Technical Field
The invention relates to the technical field of bolts, in particular to a high-strength strengthening and toughening bolt and a heat treatment process thereof.
Background
The high-strength bolt is applied to important connecting fasteners of mining machines and shield machines, the thread specification is M36-M60mm, the tensile strength can reach 1350MPa, and no proper reference standard and technical conditions exist in China at present. The bolt applies axial pre-tightening tensile load in installation, bears transverse shearing alternating load in work or bending load compounded by the transverse shearing alternating load, and is easy to generate fatigue fracture at a thread part or a transition part of the thread and a rod to cause early failure, thereby bringing huge potential safety hazards to underground continuous operation mining machines and shield tunneling machines, having high maintenance cost and seriously influencing the construction progress.
How to improve the high strength of the bolt and simultaneously have the obdurability in the aspects of material alloying and heat treatment process, and overcome the fatigue fracture of the bolt becomes a technical problem to be solved by technical personnel in the field. The patent (202010314474.9) discloses a heat treatment method for a delayed fracture-resistant high-strength bolt, which is a heat treatment process method that the material is 42CrMoA, the temperature is slowly raised through steps, then the temperature is rapidly raised to austenitize, and then the temperature is quenched and reduced twice. The method can effectively refine crystal grains and improve the impact toughness of the bolt, but the technology adopts double-liquid cooling, has strict requirements on cooling speed, is not easy to control and has high production difficulty.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a high-strength strengthening and toughening bolt and a heat treatment process thereof, and aims to solve the problem of early fatigue fracture of the high-strength bolt for the existing mining machine and the shield machine. The invention greatly improves the performance of the high-strength bolt applied to the important connecting fastener driven by the mining machine and the shield machine main through the innovation of material selection and heat treatment process, effectively solves the problems of poor hardenability and deformation cracking of the large-diameter bolt in quenching, and simultaneously ensures that the bolt has high toughness under high strength through a grain refining means.
The technical scheme adopted by the invention for solving the technical problems is as follows: a high-strength strengthening-toughening bolt is made of medium-carbon multi-element alloy structural steel and comprises the following chemical components in percentage by mass: c:0.26 to 0.36%, si:0.17 to 0.37%, mn:0.50 to 0.80%, P: less than or equal to 0.015%, S: less than or equal to 0.015 percent, cr:1.3 to 2.2%, ni:1.3 to 2.2%, mo:0.15 to 0.50%, al: 0.015-0.030%, and the balance of Fe and impurities.
The invention also provides a heat treatment process of the high-strength strengthening and toughening bolt, which comprises the following steps:
step one, pre-induction normalizing of the bolt:
secondly, placing the bolts in a continuous mesh belt quenching furnace, wherein the quenching temperature is 820-900 ℃, the time in the furnace is 50-60min, and the cooling medium is inorganic aqueous solution;
thirdly, placing the bolts in a continuous mesh belt tempering furnace, wherein the tempering temperature is 500-550 ℃, the time in the furnace is 90-120min, and the cooling medium is water;
fourthly, placing the bolt in a well-type tempering furnace, heating the bolt from room temperature to 500-550 ℃, keeping the temperature for 75-105min, and taking air as a cooling medium;
and step five, finishing the heat treatment to obtain a semi-finished product before thread rolling.
Compared with the prior art, the invention has the positive effects that:
the invention pre-normalizes the workpiece, has short induction heating time, effectively refines crystal grains, eliminates stress and simultaneously makes organization preparation for quenching. The workpiece is placed in a continuous mesh belt quenching furnace, the temperature is equalized at 820 ℃, the temperature is quickly raised to 900 ℃, the homogenization of austenite of the material can be promoted, the temperature is lowered to 820 ℃, the growth of austenite grains is effectively avoided, and the quenching stress is reduced.
The invention adopts inorganic aqueous solution, the cooling characteristic at 400-600 ℃ is close to that of water, the stability of austenite structure is ensured, the cooling characteristic at 300 ℃ is close to that of oil, and the stress in the quenching process is reduced. The quenching process improves the hardenability of the bolt, solves the problem of imperceptibility of the center of the large-diameter workpiece, and avoids the phenomena of deformation and cracking.
The invention adopts secondary tempering, is beneficial to Mo and other elements in the matrix to form MC type carbide, and is dispersed and precipitated in large quantity and uniformly distributed in the matrix, thereby preventing the strength of the material from being further reduced and simultaneously improving the impact toughness of the material.
At present, the high-strength bolt applied to mining machines and shield machines in China has no clear reference standard and technical conditions, and the tensile strength of the bolt obtained by the invention can reach 1350MPa and the impact absorption power KV at the temperature of-20 ℃ after the heat treatment by referring to the contents of the fastener mechanical property standard GB/T3098.1 2 The performance of the bolt is far superior to 10.9 or 12.9 grade in the standard, and no fatigue fracture failure occurs in use.
Detailed Description
The bolt material is medium-carbon multi-element alloy structural steel, and comprises the following chemical components in percentage by mass: c:0.26 to 0.36%, si:0.17 to 0.37%, mn:0.50 to 0.80%, P: less than or equal to 0.015%, S: less than or equal to 0.015 percent, cr:1.3 to 2.2%, ni:1.3 to 2.2%, mo:0.15 to 0.50%, al:0.015 to 0.030 percent, and the balance of Fe and inevitable impurities. Further, when the tensile strength of the bolt is more than or equal to 1300MPa, the content of each element C:0.26 to 0.31%, cr:1.8 to 2.2%, ni:1.8 to 2.2%, mo:0.30 to 0.50 percent; when the tensile strength of the bolt is 1150-1300 MPa, the content of each element C:0.31 to 0.36%, cr:1.3 to 1.8%, ni:1.3 to 1.8%, mo:0.15 to 0.30 percent. Compared with the common high-strength bolt made of 42CrMoA or 40CrNiMo, the high-strength bolt disclosed by the invention has the advantages that the content of C element is reduced on the material selection, the multi-element alloying of Cr, ni, mo and AL elements is added, the dislocation strengthening effect is improved by refining crystal grains, the tempering temperature is increased as far as possible under the condition of ensuring high strength, and the strengthening and toughening are realized.
The heat treatment process comprises the following steps:
s1, pre-induction normalizing of bolts:
the bolt is heated by ultrasonic frequency induction, and is cooled by air after the temperature of the bolt reaches 1050 ℃;
s2, placing the bolt in a continuous mesh belt quenching furnace, wherein the quenching temperature is 820-900 ℃, the time in the furnace is 50-60min, and the cooling medium is an inorganic aqueous solution, wherein:
(1) The set temperature of the continuous mesh belt quenching furnace 1-6 is 820-820-860-900-820 ℃ respectively.
(2) The baume degree of the inorganic aqueous solution is 10-13 ℃, and the temperature is controlled at 20-40 ℃;
s3, placing the bolt in a continuous mesh belt tempering furnace, wherein the tempering temperature is 500-550 ℃, the time in the furnace is 90-120min, and the cooling medium is water, wherein: setting temperatures of 1-6 areas of the continuous mesh belt tempering furnace are the same;
s4, placing the bolt in a well type tempering furnace, heating to 500-550 ℃ from room temperature, keeping the temperature for 75-105min, and taking air as a cooling medium; wherein: the bolt is vertically placed in a well type tempering furnace after being straightened and machined, and is protected by methanol atmosphere.
And S5, finishing the heat treatment to obtain a semi-finished product before thread rolling.
In order to make the technical solutions and advantages of the present application clearer, the present invention is further explained below with reference to specific embodiments.
Example one
A high-strength bolt for a mining machine comprises the following chemical components: 0.31%, si:0.28%, mn:0.57%, P:0.011%, S:0.007%, cr:2.06%, ni:2.15%, mo:0.36%, al:0.021 percent. The heat treatment process comprises the following steps:
s1, pre-induction normalizing of the bolt.
Specifically, the workpiece is heated by ultrasonic frequency induction, and is cooled by air after the temperature reaches 1050 ℃.
S2, placing the workpiece in a continuous mesh belt quenching furnace for quenching treatment.
Specifically, the temperature of the 1-6 area of the continuous mesh belt quenching furnace is set to be 820-820-860-900-820-820 ℃, the furnace is charged at room temperature, and the time in the furnace is 50min; the cooling medium is inorganic aqueous solution with Baume degree of 11.5 deg.C, and the temperature is controlled at 20-40 deg.C.
S3, placing the workpiece in a continuous mesh belt tempering furnace for tempering treatment.
Specifically, the temperature is set to be 500 ℃ in a 1-6 area of a continuous mesh belt tempering furnace, and the time in the furnace is 90min; the cooling medium is water, and the water temperature is controlled at 20-50 ℃.
And S4, placing the workpiece in a well type tempering furnace for secondary tempering treatment.
Specifically, the workpiece is vertically placed in a well type tempering furnace after being straightened and machined, the temperature is raised to 500 ℃ from room temperature, and the heat preservation time is 75min; discharging and air cooling; preferably, the secondary tempering is protected by a methanol atmosphere.
And S5, finishing the heat treatment to obtain a semi-finished product before thread rolling.
The bolt after the heat treatment has the tensile strength of 1350MPa, the elongation of 15 percent, the reduction of area of 57 percent and the impact absorption power KV at the temperature of minus 20 DEG C 2 The bolt strength reaches 85J, the strength grade of the bolt is far superior to 12.9 grades in GB/T3098.1, and no fatigue fracture failure occurs in use.
Example two
A high-strength bolt for a shield machine comprises the following chemical components of 0.33% of C, si:0.33%, mn:0.66%, P:0.012%, S:0.009%, cr:1.47%, ni:1.45%, mo:0.18%, al:0.020%. The heat treatment process comprises the following steps:
s1, pre-induction normalizing of the bolt.
The specific workpiece is heated by ultrasonic frequency induction, and is cooled by air after the temperature reaches 1050 ℃.
S2, placing the workpiece in a continuous mesh belt quenching furnace for quenching treatment.
Specifically, the set temperature of the 1-6 areas of the continuous mesh belt quenching furnace is 820-820-860-900-820-820 ℃, the furnace is charged at room temperature, and the time in the furnace is 60min; the cooling medium is inorganic aqueous solution with Baume degree of 10.5 deg.C, and the temperature is controlled at 20-40 deg.C.
S3, placing the workpiece in a continuous mesh belt tempering furnace for tempering treatment.
Specifically, the temperature of a 1-6 area of a continuous mesh belt tempering furnace is set to be 550 ℃, and the time in the furnace is 120min; the cooling medium is water, and the water temperature is controlled at 20-50 ℃;
and S4, placing the workpiece in a well type tempering furnace for secondary tempering treatment.
Specifically, the workpiece is vertically placed in a well type tempering furnace after being straightened and machined, the temperature is raised to 550 ℃ from room temperature, and the heat preservation time is 105min; discharging and air cooling; preferably, the secondary tempering is protected by a methanol atmosphere.
And S5, finishing the heat treatment to obtain a semi-finished product before thread rolling.
The bolt after the heat treatment has the tensile strength of 1198MPa, the elongation of 17 percent, the reduction of area of 60 percent and the impact absorption power KV of-20 DEG C 2 The bolt strength grade is far superior to 10.9 grade in GB/T3098.1, and no fatigue fracture failure occurs in use.

Claims (10)

1. A high-strength strengthening and toughening bolt is characterized in that: the material is medium-carbon multi-component alloy structural steel, and comprises the following chemical components in percentage by mass: c:0.26 to 0.36%, si:0.17 to 0.37%, mn:0.50 to 0.80%, P: less than or equal to 0.015 percent, S: less than or equal to 0.015 percent, cr:1.3 to 2.2%, ni:1.3 to 2.2%, mo:0.15 to 0.50%, al:0.015 to 0.030 percent, and the balance of Fe and impurities.
2. The high-strength toughened bolt as claimed in claim 1, wherein: when the tensile strength of the bolt is more than or equal to 1300MPa, the contents of all elements are as follows: c:0.26 to 0.31%, cr:1.8 to 2.2%, ni:1.8 to 2.2%, mo:0.30 to 0.50 percent.
3. The high strength, tough bolt according to claim 1, wherein: when the tensile strength of the bolt is 1150-1300 MPa, the contents of the elements are as follows: c:0.31 to 0.36%, cr:1.3 to 1.8%, ni:1.3 to 1.8%, mo:0.15 to 0.30 percent.
4. A heat treatment process of a high-strength strengthening and toughening bolt is characterized in that: the method comprises the following steps:
step one, pre-induction normalizing of a bolt:
secondly, placing the bolt in a continuous mesh belt quenching furnace, wherein the quenching temperature is 820-900 ℃, the time in the furnace is 50-60min, and the cooling medium is an inorganic aqueous solution;
thirdly, placing the bolt in a continuous mesh belt tempering furnace, wherein the tempering temperature is 500-550 ℃, the time in the furnace is 90-120min, and the cooling medium is water;
fourthly, placing the bolt in a well-type tempering furnace, heating the bolt from room temperature to 500-550 ℃, keeping the temperature for 75-105min, and taking air as a cooling medium;
and step five, finishing the heat treatment to obtain a semi-finished product before thread rolling.
5. The heat treatment process for the high-strength toughened bolt according to claim 4, wherein: the method for pre-induction normalizing comprises the following steps: and (3) performing ultrasonic frequency induction heating on the bolt to enable the temperature of the bolt to reach 1050 ℃, and then performing air cooling.
6. The heat treatment process of the high-strength toughened bolt according to claim 4, wherein: setting the temperatures of the areas 1 to 6 of the continuous mesh belt quenching furnace in the step two as follows: 820 deg.C, 860 deg.C, 900 deg.C, 820 deg.C.
7. The heat treatment process of the high-strength toughened bolt according to claim 4, wherein: in the second step, the Baume degree of the inorganic aqueous solution is 10-13 ℃, and the temperature is controlled to be 20-40 ℃.
8. The heat treatment process of the high-strength toughened bolt according to claim 4, wherein: and step three, setting the same temperature in the areas 1-6 of the continuous mesh belt tempering furnace.
9. The heat treatment process of the high-strength toughened bolt according to claim 4, wherein: and in the fourth step, the bolt is straightened and machined and then vertically placed in a well type tempering furnace.
10. The heat treatment process of the high-strength toughened bolt according to claim 4, wherein: and step four, adopting a methanol atmosphere for protection in the well type tempering furnace.
CN202211377421.7A 2022-11-04 2022-11-04 High-strength toughened bolt and heat treatment process thereof Pending CN115679227A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211377421.7A CN115679227A (en) 2022-11-04 2022-11-04 High-strength toughened bolt and heat treatment process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211377421.7A CN115679227A (en) 2022-11-04 2022-11-04 High-strength toughened bolt and heat treatment process thereof

Publications (1)

Publication Number Publication Date
CN115679227A true CN115679227A (en) 2023-02-03

Family

ID=85049957

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211377421.7A Pending CN115679227A (en) 2022-11-04 2022-11-04 High-strength toughened bolt and heat treatment process thereof

Country Status (1)

Country Link
CN (1) CN115679227A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851479A (en) * 2011-06-29 2013-01-02 徐州市瑞达高强度紧固件厂 Heat treatment technology of high-strength bolt
CN103266212A (en) * 2013-05-31 2013-08-28 中原特钢股份有限公司 Thermal treatment technology for improving low-temperature impact toughness of 25Cr2Ni4MoV steel forging
CN105506496A (en) * 2014-09-24 2016-04-20 上海宝钢工业技术服务有限公司 High-strength prestressing force bolt production method
CN105907938A (en) * 2016-05-05 2016-08-31 太仓小小精密模具有限公司 Heat treatment technology of high-strength bolt
CN106048152A (en) * 2016-07-24 2016-10-26 钢铁研究总院 Thermal treatment method for improving low-temperature impact toughness of rods
CN110283969A (en) * 2019-06-14 2019-09-27 洛阳双瑞特种装备有限公司 A kind of high-intensity fasteners preparation method
CN110468341A (en) * 2019-08-13 2019-11-19 南京钢铁股份有限公司 A kind of 1400MPa grades of delayed fracture resistance high-strength bolt and manufacturing method
CN111424140A (en) * 2020-04-21 2020-07-17 安徽长江紧固件有限责任公司 Heat treatment method for delayed fracture-resistant high-strength bolt
CN112553434A (en) * 2020-12-04 2021-03-26 西京学院 Low-temperature-toughness Ni-Mo-Cr series steel and pre-heat treatment process
CN114941104A (en) * 2022-05-09 2022-08-26 河南中原特钢装备制造有限公司 Ultrahigh-strength 30CrNi2MoV forging drilling tool material and heat treatment process

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851479A (en) * 2011-06-29 2013-01-02 徐州市瑞达高强度紧固件厂 Heat treatment technology of high-strength bolt
CN103266212A (en) * 2013-05-31 2013-08-28 中原特钢股份有限公司 Thermal treatment technology for improving low-temperature impact toughness of 25Cr2Ni4MoV steel forging
CN105506496A (en) * 2014-09-24 2016-04-20 上海宝钢工业技术服务有限公司 High-strength prestressing force bolt production method
CN105907938A (en) * 2016-05-05 2016-08-31 太仓小小精密模具有限公司 Heat treatment technology of high-strength bolt
CN106048152A (en) * 2016-07-24 2016-10-26 钢铁研究总院 Thermal treatment method for improving low-temperature impact toughness of rods
CN110283969A (en) * 2019-06-14 2019-09-27 洛阳双瑞特种装备有限公司 A kind of high-intensity fasteners preparation method
CN110468341A (en) * 2019-08-13 2019-11-19 南京钢铁股份有限公司 A kind of 1400MPa grades of delayed fracture resistance high-strength bolt and manufacturing method
CN111424140A (en) * 2020-04-21 2020-07-17 安徽长江紧固件有限责任公司 Heat treatment method for delayed fracture-resistant high-strength bolt
CN112553434A (en) * 2020-12-04 2021-03-26 西京学院 Low-temperature-toughness Ni-Mo-Cr series steel and pre-heat treatment process
CN114941104A (en) * 2022-05-09 2022-08-26 河南中原特钢装备制造有限公司 Ultrahigh-strength 30CrNi2MoV forging drilling tool material and heat treatment process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
中国国家标准化管理委员会: "《中国人民共和国国家标准GB/T 3077-2015——合金结构钢》", 国防工业出版社, pages: 83 *

Similar Documents

Publication Publication Date Title
CN107385329A (en) A kind of big thickness Q500GJE high-strength buildings structural steel plate and its manufacture method
CN109252107B (en) Production method of high-flatness ultrahigh-strength steel
CN110791715A (en) Niobium-titanium-containing atmospheric corrosion-resistant 14.9-grade high-strength bolt steel and production method thereof
CN111041356B (en) Niobium-containing atmospheric corrosion-resistant 14.9-grade high-strength bolt steel and production method thereof
CN106811580A (en) A kind of annealing process of H13 hot die steels
CN112322867B (en) Heat treatment process for improving comprehensive mechanical properties of Cr-Ni-Mo large-scale forging for nuclear power
CN102876999A (en) Steel plate for hardening and tempering type low temperature pressure vessel and method for producing steel plate
CN102080190A (en) Hardening and tempering steel plate for engineering machinery with 7000MPa grade yield strength and preparation method thereof
CN112981277B (en) Preparation method of ultrahigh-strength medium-carbon nano bainite steel
CN101624683A (en) Ultra-high strength bainite rail steel and manufacturing method thereof
CN110938732A (en) Titanium-containing atmospheric corrosion-resistant 14.9-grade high-strength bolt steel and production method thereof
JP2024503015A (en) High-strength, high-toughness, easy-to-cut unhardened and tempered round steel and its manufacturing method
CN111910134B (en) High-strength high-toughness spring steel used under high-temperature and high-pressure conditions and production method thereof
CN110358970B (en) Welded structure bainite high-strength steel with yield strength of 1100MPa and preparation method thereof
CN112048668B (en) High-hardness steel for shield cutter and manufacturing method thereof
CN116904836A (en) Preparation method of high-hardness high-toughness bainite wear-resistant steel
CN115747678B (en) Steel for high-strength bolt for wind power and high-strength bolt for wind power
CN115627423B (en) 1600 MPa-grade hot rolled coil and production method thereof
CN115679227A (en) High-strength toughened bolt and heat treatment process thereof
CN111910127B (en) Q890 steel plate for hydraulic support meeting welding heat input of 30kJ/cm and preparation method thereof
CN114959424A (en) Production method of anti-deformation wear-resistant steel
CN115233503A (en) Medium-strength steel rail with high yield strength and production method thereof
CN110396641B (en) Non-quenched and tempered HB 360-grade medium plate wear-resistant steel with good hardenability and production method thereof
CN107267880A (en) A kind of high cracking resistance wear-resistant bainite Jaw plate steel, Jaw plate and preparation method
CN111500943A (en) 10.9-grade medium-carbon non-quenched and tempered fastener and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination