CN117491149A - Method for measuring tensile property of high-hardness vulcanized rubber - Google Patents
Method for measuring tensile property of high-hardness vulcanized rubber Download PDFInfo
- Publication number
- CN117491149A CN117491149A CN202311454388.8A CN202311454388A CN117491149A CN 117491149 A CN117491149 A CN 117491149A CN 202311454388 A CN202311454388 A CN 202311454388A CN 117491149 A CN117491149 A CN 117491149A
- Authority
- CN
- China
- Prior art keywords
- test
- hardness
- vulcanized rubber
- tensile
- sample
- 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
Links
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000012360 testing method Methods 0.000 claims abstract description 68
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- 238000009864 tensile test Methods 0.000 claims description 10
- 230000036316 preload Effects 0.000 claims description 6
- 241000283690 Bos taurus Species 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000013101 initial test Methods 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/02—Details
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/02—Details
- G01N3/04—Chucks
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Strength Of Materials By Application Of Mechanical Stress (AREA)
Abstract
The invention discloses a method for measuring tensile property of high-hardness vulcanized rubber, and belongs to the technical field of analysis. According to the rubber with the hardness exceeding 70 Shore A hardness or 70 International hardness number after vulcanization, the size of a test sample is adjusted according to the hardness difference of the vulcanized rubber, the test sample comprises the width, the length and the thickness of the test sample, the test sample is cut into strip-shaped test samples with the width of 8mm, 10mm or 12mm, the thickness of 2mm and the length of 200mm, so that the tensile strength, the elongation at break and the 300% stretching result can truly represent the physical properties of the rubber, and the defect that the physical properties (strength, elongation and stretching) of the rubber cannot be truly represented due to the fact that the test is carried out by using dumbbell test samples or rings and other test samples in the traditional method, and the rubber with the large hardness number is too small in tensile strength and too fast in breaking.
Description
Technical Field
The invention belongs to the technical field of analysis, and particularly relates to a method for measuring tensile properties of high-hardness vulcanized rubber.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The tensile property of vulcanized rubber is the most important item in the test of mechanical properties of rubber, and is one of effective methods for identifying the vulcanization property of rubber products. At present, the tensile property of vulcanized rubber is mainly detected according to GB/T528-2009, and the tensile strength, elongation at break and 300% elongation of the vulcanized rubber are measured according to dumbbell samples or rings and other samples in the standard. However, in practical production, some vulcanized rubber with larger hardness, such as rubber with hardness exceeding 70 Shore A hardness or 70 International hardness value after vulcanization, is hard and difficult to prepare a sample when a standard dumbbell sample or a ring and other samples are adopted for tensile test, and has the defects that the tensile strength is too small, the breaking is too fast, the tensile strength, the elongation at break and the 300% elongation are caused, and the physical properties (strength, elongation and elongation) of the rubber material cannot be truly represented as a test result. Therefore, a method capable of precisely detecting the tensile properties of high-hardness vulcanized rubber is highly demanded.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the method for measuring the tensile properties of the vulcanized rubber with high hardness.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for measuring tensile properties of a high-hardness vulcanized rubber, comprising the steps of:
(1) According to a test formula of the test rubber design, preparing rubber compound and vulcanizing to obtain a vulcanized test piece;
(2) Cutting the vulcanized test piece into strip-shaped test pieces with different widths by using a cutting knife according to different hardness of the vulcanized rubber; wherein the corresponding relation between the international hardness and the width of the strip sample is: the international hardness IRHD is: 70 and above, the width of the strip sample is: 8mm-12mm, the thickness of the strip sample is as follows: 2mm + -0.2 mm, the strip sample length is: more than or equal to 200mm;
(3) And fixing the strip-shaped sample into a clamp of a tensile testing machine, starting a test after clamping the fixed sample, and recording tensile strength, tensile elongation and stretching stress data.
In some embodiments of the present invention, for further accuracy of the tensile property test of the high-hardness vulcanized rubber, the international hardness versus the width of the strip specimen is shown in the following table.
| International hardness IRHD | Width of sample |
| 70-80 | 8mm±0.1mm |
| 80-85 | 10mm±0.1mm |
| 85 or more | 12mm±0.1mm |
In some embodiments of the invention, the post-cure sample parking time is at least 16 hours and should not exceed 4 weeks at maximum. Meanwhile, the comparison evaluation test should be performed as much as possible within the same time interval.
In some embodiments of the invention, the parking is carried out in the absence of light, and the sample is conditioned at standard temperature (without humidity control) for at least 3 hours as specified in GB/T2941 prior to trimming the test piece. The specimens can also be insulated during parking to protect them as completely as possible from extraneous influences which might lead to damage during the time interval between vulcanization and testing.
In some embodiments of the invention, the strip is cut parallel to the calendering direction of the vulcanized rubber.
In some embodiments of the present invention, when testing with a tensile tester, the test conditions are: the stretching speed is 50mm/min-300mm/min, the original clamp distance is 25mm-100mm, the pre-load is 0.5-1N, and the stretching speed is 20-50mm/min under the pre-load.
In some embodiments of the invention, at least five samples were tailored for each test, tensile strength, tensile elongation, tensile stress data were recorded, and the final result was an average of 5 samples.
In some embodiments of the invention, the test results are discarded if the test specimen breaks at the nip of the original clamp, and another test specimen is taken for repeated testing.
In some embodiments of the invention, the tensile strength T is calculated as expressed in MPa according to the formula:
F m : maximum force recorded in bovine (N);
w: the width of the sample in millimeters (mm);
t: test length part thickness in millimeters (mm).
In some embodiments of the invention, elongation at break E b Calculated as% by:
L 0 : initial test length in millimeters (mm);
L b : test length at break in millimeters (mm).
In some embodiments of the invention, the stress at elongation Se is calculated as follows, expressed in MPa:
F e : force recorded at a given stress in newtons (mm);
w: the width of the sample in millimeters (mm);
t: test length part thickness in millimeters (mm).
The beneficial effects of the invention are as follows:
the invention discloses a method for measuring the tensile property of high-hardness vulcanized rubber, which is characterized in that a cutter is selected to cut samples with different widths according to different hardness of vulcanized rubber, wherein the widths can be respectively as follows: 8mm + -0.1 mm, 10mm + -0.1 mm, 12mm + -0.1 mm, thick: 2mm + -0.2 mm, length: about 200mm (where 100mm is used for testing), at least five specimens were cut; and then a tensile testing machine is adopted to carry out tensile testing at a proper speed. The invention solves the problem that the physical properties (strength, elongation and elongation) of the sizing material cannot be truly represented due to the tensile strength, elongation at break and 300% elongation determination results caused by too small tensile strength and too fast fracture when the sizing material with high hardness is subjected to tensile test by adopting dumbbell samples or rings and other samples of GB/T528-2009. The invention provides a method for measuring the tensile stress strain performance of vulcanized rubber with larger hardness by adopting strip-shaped stretching, which is very simple, convenient and quick, can adjust the width of a sample according to the hardness, and expands the application range of tensile strength, elongation at break and 300% definite elongation. The method is simple and feasible, has high reproducibility, improves the detection accuracy, and effectively solves the problem that the tensile property of the sizing material with larger hardness cannot be accurately reflected in GB/T528-2009. In actual production, the formula, the mixing process, the vulcanization process and the like can be adjusted according to the detection result of the tensile property, so that the stability of the rubber quality is ensured.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a bar sample shape diagram of the present invention;
FIG. 2 is a tensile stress strain curve of a bar sample of example 2 of the present invention;
FIG. 3 is a tensile stress strain curve of a type 1 dumbbell specimen of comparative example 1 of the present invention.
Detailed Description
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
(1) Sample:
the curing conditions of the compound are selected to be optimal (time, temperature and pressure) depending on the rheological properties of the compound. The sample parking time after vulcanization is 16h at the shortest and should not exceed 4 weeks at the longest. It should be stored protected from light during its parking and adjusted at standard temperature for at least 3 hours as specified in GB/T2941 before tailoring the sample.
According to the hardness of the vulcanized rubber, the rubber is cut into samples with different widths by a cutter according to the corresponding relation in the table 1, and the widths can be respectively: 8mm + -0.1 mm, 10mm + -0.1 mm, 12mm + -0.1 mm, thick: 2mm + -0.2 mm, length: about 200mm (100 mm of which is used for testing), the length of the specimen at both ends of the clamp before stretching is 100mm, at least five specimens are cut, and the strip-shaped specimens are cut parallel to the calendering direction of the vulcanized rubber.
TABLE 1 International hardness and sample width correspondence
| International hardness IRHD | Width of sample |
| 70-80 | 8mm±0.1mm |
| 80-85 | 10mm±0.1mm |
| 85 or more | 12mm±0.1mm |
Measurement of sample thickness: thickness was measured with a thickness gauge at 25mm at the center and both ends of the center of the test specimen, and the median value of the three values was taken as the thickness result, and the difference between the maximum value and the minimum value and the median value should not exceed + -0.1 mm. Measurement of sample width: the width of the test sample is measured by a digital vernier caliper at the center and two ends 25mm of the center of the effective test sample, and the median value of the three values is taken as the width of the sample, so that the accuracy is 0.05mm.
(2) The test process comprises the following steps:
and (3) setting tensile testing machine software: the stretching speed is 300mm/min, the original clamp distance is 100mm, the pre-load is 0.5-1N, and the stretching speed is 20-50mm/min when the pre-load is performed. After clamping the fixed samples, the clamp distance l=100 mm±0.2mm was adjusted, the test was started, tensile strength, tensile elongation and tensile stress data were recorded, and the final result was an average value of 5 samples. If the sample breaks beyond the original clamp, the test results are discarded and another sample is taken for repeated testing.
(3) Results expression
Tensile strength T is calculated according to the formula and expressed in MPa:
F m : maximum force recorded in bovine (N);
w: the width of the sample in millimeters (mm);
t: test length part thickness in millimeters (mm).
Elongation at break E b Calculated as% by:
L 0 : initial test length in millimeters (mm);
L b : test length at break in millimeters (mm).
Stress S of definite elongation e Calculated as MPa:
F e : the force recorded given the stress is in bovine (N);
w: the width of the sample in millimeters (mm);
t: test length part thickness in millimeters (mm).
Example 2
Tensile properties were tested using 3 different durometer vulcanized gums A, B, C, with the formulation of vulcanized gum A, B, C shown in table 2.
Table 2 formulation of vulcanized rubber A, B, C
| Material | Vulcanized rubber A | Vulcanized rubber B | Vulcanized rubber C |
| Natural glue | 100 | 100 | 100 |
| Carbon black N220 | 53 | 60 | 65 |
| Stearic acid | 3.5 | 3.5 | 3.5 |
| Zinc oxide | 2 | 2 | 2 |
| Plasticizer A | 1 | 1 | 1 |
| Peptizer B | 0.3 | 0.3 | 0.3 |
| Protective wax | 1 | 1 | 1 |
| Accelerator NS | 1 | 1 | 1 |
| Sulfur, sulfur and its preparation method | 1.5 | 1.5 | 1.5 |
| Totalizing | 163.3 | 170.3 | 175.3 |
The hardness of the vulcanized rubber A was measured to be IRHD70-80, and a bar-shaped test piece with a width of 8mm, a thickness of 2mm and a length of 200mm was cut according to the method of example 1, and the test results are shown in Table 3, and the tensile stress strain curve is shown in FIG. 2.
The hardness of the vulcanized rubber B was IRHD80-85, and a strip-shaped test piece with the width of 10mm, the thickness of 2mm and the length of 200mm was cut according to the method of example 1, and the test result is shown in Table 3, and the tensile stress strain curve is shown in FIG. 2.
The hardness of the vulcanized rubber C was not less than IRHD85, and a bar-shaped test piece having a width of 12mm, a thickness of 2mm and a length of 200mm was cut according to the method of example 1, and the test results are shown in Table 3, and the tensile stress strain curve is shown in FIG. 2.
Comparative example 1
The three compounds of example 2 were cut into dumbbell type 1 test pieces according to the method of GB/T528-2009, and then subjected to tensile test, the test results are shown in Table 3, and the tensile stress strain curves are shown in FIG. 3.
TABLE 3 tensile Property test results of high hardness vulcanized rubber
Analysis:
data stability is used to make a very poor comparison of data. As is clear from Table 2, the detection method of the present invention has high reproducibility and higher detection accuracy. On the one hand, the dumbbell sample and the circular ring sample are special in shape, the structure of the sample is easy to break when the sample is manufactured, tooth marks are easy to appear at the edge of the sample, and the tensile test result of the sample is inaccurate. The strip-type sample is simple to prepare, the structure of the sample is prevented from being damaged, and the accuracy of a tensile test result is ensured. On the other hand, the width of the sample can be properly adjusted according to different hardness, so that the application range is ensured to be wider.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for measuring the tensile property of the high-hardness vulcanized rubber is characterized by comprising the following steps of:
(1) According to a test formula of the test rubber design, preparing rubber compound and vulcanizing to obtain a vulcanized test piece;
(2) Cutting the vulcanized test piece into strip-shaped test pieces with different widths by using a cutting knife according to different hardness of the vulcanized rubber; wherein the corresponding relation between the international hardness and the width of the strip sample is: the international hardness IRHD is: 70 and above, the width of the strip sample is: 8mm-12mm, the thickness of the strip sample is as follows: 2mm + -0.2 mm, the strip sample length is: more than or equal to 200mm;
(3) And fixing the strip-shaped sample into a clamp of a tensile testing machine, starting a test after clamping the fixed sample, and recording tensile strength, tensile elongation and stretching stress data.
2. The method for measuring the tensile properties of a high-hardness vulcanized rubber according to claim 1,
The correspondence between the international hardness and the width of the bar-shaped specimen is shown in the table.
3. The method for measuring the tensile properties of a high-hardness vulcanized rubber according to claim 1, wherein the specimen has a residence time of at least 16 hours and at most 4 weeks after vulcanization;
preferably, the said shelf is stored in a dark place, and the sample is conditioned at standard temperature for at least 3 hours according to GB/T2941 before the vulcanized test piece is cut.
4. The method for measuring the tensile properties of a high-hardness vulcanized rubber according to claim 1, wherein the strip-shaped specimen is cut parallel to the rolling direction of the vulcanized rubber.
5. The method for measuring the tensile properties of high-hardness vulcanized rubber according to claim 1, wherein when the test is performed by a tensile tester, the test conditions are as follows: the stretching speed is 50mm/min-300mm/min, the original clamp distance is 25mm-100mm, the pre-load is 0.5-1N, and the stretching speed is 20-50mm/min under the pre-load.
6. The method for measuring the tensile properties of high-hardness vulcanized rubber according to claim 1, wherein at least five samples are cut for each test, the tensile strength, tensile elongation and tensile stress data are recorded, and the average value of the 5 samples is taken as the final result.
7. The method for measuring the tensile properties of a high-hardness vulcanized rubber according to claim 6, wherein the test results are discarded when the test specimen breaks at the nip of the original jig, and a test specimen is taken for repeated tests.
8. The method for measuring the tensile properties of a high-hardness vulcanized rubber as set forth in claim 1, wherein the tensile strength T is expressed in Mpa as calculated in the formula:
F m : the maximum force recorded is in cattle;
w: the width of the sample is in millimeters;
t: the test length is in millimeters for part of the thickness.
9. The method for measuring tensile properties of a high-hardness vulcanized rubber as set forth in claim 1, whereinIn that elongation at break E b Calculated as% by:
L 0 : initial test length in millimeters;
L b : test length at break in millimeters.
10. The method for measuring the tensile properties of a high-hardness vulcanized rubber according to claim 1, wherein the stress at elongation Se is calculated as:
F e : the force recorded at a given stress is in cattle;
w: the width of the sample is in millimeters;
t: the test length is in millimeters for part of the thickness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311454388.8A CN117491149A (en) | 2023-11-02 | 2023-11-02 | Method for measuring tensile property of high-hardness vulcanized rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311454388.8A CN117491149A (en) | 2023-11-02 | 2023-11-02 | Method for measuring tensile property of high-hardness vulcanized rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117491149A true CN117491149A (en) | 2024-02-02 |
Family
ID=89668518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311454388.8A Pending CN117491149A (en) | 2023-11-02 | 2023-11-02 | Method for measuring tensile property of high-hardness vulcanized rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117491149A (en) |
-
2023
- 2023-11-02 CN CN202311454388.8A patent/CN117491149A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20030090648A1 (en) | Method for preparing a cut surface in uncured rubber samples for measuring filler dispersion | |
| CN110823602B (en) | Method for verifying indoor evaluation of tire life cycle validity degree | |
| CN117491149A (en) | Method for measuring tensile property of high-hardness vulcanized rubber | |
| US20070113671A1 (en) | Method of crack growth testing for thin samples | |
| JP6852452B2 (en) | Tire surface crack evaluation method | |
| McKenna et al. | Experiments on the small-strain behaviour of crosslinked natural rubber: 1. Torsion | |
| JPH07198642A (en) | Vulcanization characteristic tester incorporating function for measuring electrical resistance of rubber composite | |
| Gedney | Tensile testing basics, tips and trends | |
| KR101210001B1 (en) | Method of producing rosin-modified alkylphenol resin and rubber composition for tire tread comprising rosin-modified alkylphenol resin thereof | |
| CN112683997A (en) | Method for monitoring surface grinding quality of bearing ring by Barkhausen noise analysis method | |
| CN111796084B (en) | Run-flat tire support rubber, screening method thereof and tire | |
| CN111537346B (en) | Tensile strength detection method for reconstituted tobacco finished product | |
| CN211400985U (en) | Aging impact deformation measuring scale | |
| Wilchinsky et al. | A Quantitative Test for Ozone Resistance of Rubber Vulcanizates | |
| CN114428018A (en) | Method for evaluating breaking strength of water-based epoxy emulsified asphalt material | |
| CN112668156B (en) | Method for calculating storage life of nonmetallic part | |
| Ganslandt et al. | Stress relaxation tests for determination of ozone attack on rubber | |
| Carleton | Suitability of materials for photoelastic investigations | |
| Newton | Technical Classification of Crude Natural Rubber | |
| JP2012255741A (en) | Tear testing method and apparatus for vulcanized rubber and wear resistant performance evaluation method | |
| Best et al. | Wax Blooming and Exposure Cracking | |
| Selles et al. | Fatigue crack growth behavior of filled SBR compounds: Influences of several parameters and of the loading scenario | |
| Hawley | Particular requirements for plastics | |
| Sheets et al. | Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers— | |
| Clamroth et al. | Stress relaxation measurement as a high-speed method for predicting the long-term behavior of vulcanized rubber |
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 |