CN115820209A - Soft elastic abrasive particles applied to tool polishing passivation processing and preparation method thereof - Google Patents
Soft elastic abrasive particles applied to tool polishing passivation processing and preparation method thereof Download PDFInfo
- Publication number
- CN115820209A CN115820209A CN202211391321.XA CN202211391321A CN115820209A CN 115820209 A CN115820209 A CN 115820209A CN 202211391321 A CN202211391321 A CN 202211391321A CN 115820209 A CN115820209 A CN 115820209A
- Authority
- CN
- China
- Prior art keywords
- particles
- abrasive
- soft
- abrasive particles
- soft elastic
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 173
- 238000005498 polishing Methods 0.000 title claims abstract description 36
- 238000002161 passivation Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000003672 processing method Methods 0.000 title description 2
- 238000012545 processing Methods 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000011246 composite particle Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 36
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 29
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 29
- 244000043261 Hevea brasiliensis Species 0.000 claims description 22
- 229920003052 natural elastomer Polymers 0.000 claims description 22
- 229920001194 natural rubber Polymers 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 229910052580 B4C Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229920003049 isoprene rubber Polymers 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 20
- 239000003082 abrasive agent Substances 0.000 abstract description 8
- 238000005096 rolling process Methods 0.000 abstract description 4
- 238000006748 scratching Methods 0.000 abstract description 4
- 230000002393 scratching effect Effects 0.000 abstract description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 238000005520 cutting process Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 238000005488 sandblasting Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000006061 abrasive grain Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000005381 potential energy Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Abstract
The invention relates to a preparation method of soft elastic abrasive particles for tool polishing passivation processing, which comprises the steps of processing a high-molecular viscoelastic base material, preparing a multi-component abrasive, heating soft carrier particles, preparing soft carrier/hard abrasive composite particles, post-treating the soft carrier/hard abrasive composite particles and the like. The soft elastic abrasive particles are of a core-shell-like structure, wherein hard abrasive materials are uniformly embedded on the surface of a soft carrier. When the abrasive particles are used for carrying out polishing and passivation processing on the surface of the cutter, the soft carrier of the abrasive particles can deform when the abrasive particles collide with the surface of the cutter, so that the abrasive particles generate certain scratching, rolling and plowing effects on the surface of the cutter, a surface material is removed finely, and finally high-efficiency and high-precision polishing and passivation integrated processing is realized.
Description
Technical Field
The invention belongs to the technical field of manufacturing of flexible abrasive particles, and particularly relates to a preparation method of soft elastic abrasive particles, in particular to soft elastic abrasive particles applied to polishing and passivation integrated processing of hard alloys and superhard material cutters and a preparation method thereof.
Background
The cutter passivation technology is one of essential procedures in the manufacturing process of modern cutters as a cutting edge post-processing technology. The processing technology is a processing process which adopts a proper process method to eliminate various defects of the cutting edge and the micro-area of the cutting edge and obtains proper microcosmic geometric parameters and surface appearance of the cutting edge. Through cutter passivation treatment, can eliminate blade residual stress, improve blade intensity, increase the coating adhesive force, promote blade wearability, finally improve the stability and the life-span of cutter.
At present, the types and technological methods of the mature tool passivation technology at home and abroad mainly comprise an abrasive brush method, a vertical rotation method, a micro-abrasive sand blasting method and a magnetic powder passivation method. The grinding material brush method for passivating the rotary cutter can generate the defect of uneven radius of the cutting edge, and the passivation quality is not stable enough; the vertical rotation method has the phenomenon that the radius of the cutting edge is not uniform along the axial direction, the polishing effect on the superhard cutter is limited, and the surface of the cutter is not uniformly polished; the micro-abrasive sand blasting method can etch the surface of the superhard material cutter, so that the surface smoothness is reduced; the contour cutter can not be processed by the magnetic powder passivation method, the outer diameter of the cutter is changed to be large, and the price is high.
In conclusion, the existing tool surface treatment technology has low processing efficiency and poor processing precision; hard alloy and superhard material cutters cannot be considered; the passivation and polishing integrated processing is difficult to be integrated, the quality is uniform and stable, and the like. Therefore, the research and the invention of the soft elastic abrasive particles for high-quality, high-efficiency, polishing and passivating integrated processing of the cutter are the core content of the invention.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides soft elastic abrasive particles which are of a core-shell-like structure and are uniformly embedded on the surface of a soft carrier by hard abrasive materials and are applied to tool polishing passivation processing. When the abrasive particles are used for carrying out surface treatment on the cutter, the abrasive particles collide with the surface of the cutter, and the soft carrier can deform, so that the abrasive particles generate certain scratching, rolling and plowing effects on the surface of the cutter, the surface material is subjected to fine removal, and finally, high-efficiency and high-precision polishing and passivation integrated processing is realized.
The second purpose of the invention is to provide a preparation method of the soft elastic abrasive particles applied to the tool polishing passivation processing.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing soft elastic abrasive particles for tool polishing passivation processing comprises the following steps:
s1, processing of a high-molecular viscoelastic base material: crushing and screening the high-molecular viscoelastic base material master batch to obtain soft carrier particles with a target shape within a target particle size range;
s2, preparing a multi-component abrasive: mixing and screening a certain proportion of superhard abrasive and ordinary abrasive to obtain uniformly dispersed multicomponent abrasive;
s3, heating soft carrier particles: pouring the soft carrier particles prepared in the step S1 into a heatable mixing device, stirring for a certain time at a certain temperature, and ensuring that the soft carrier particles generate viscous flow transformation to a certain degree on the surfaces of the soft carrier particles under the condition of no agglomeration through the continuous rotary stirring and heating action of the device;
s4, preparing soft carrier/hard abrasive composite particles: uniformly pouring the multicomponent abrasive of S2 into the soft carrier particle system obtained in S3 according to a certain proportion, continuously stirring for a certain time by a heatable mixing device to ensure that the hard abrasive is compacted and uniformly distributed on the surface of the soft carrier, and preparing to obtain soft carrier/hard abrasive composite particles;
s5, post-treatment of the soft carrier/hard abrasive composite particles: and (4) collecting the composite particles prepared in the step (S4), placing the composite particles in a room temperature environment for a certain time, and repeatedly screening to obtain the soft elastic abrasive particles with the target particle size range and the target shape.
Specifically, in the step S1, the shore hardness of the polymer viscoelastic base material master batch is less than or equal to 70HA, and the density range is 0.6-2.2g/cm 3 (ii) a The high molecular viscoelastic base material can be selected from Natural Rubber (NR), isoprene Rubber (IR), polyurethane rubber (PUR), styrene thermoplastic elastomer (TPES), thermoplastic Polyurethane (TPU), and ethylene-vinyl acetate copolymerOne or more of a copolymer and a polyolefin elastomer (POE).
Further, in the step S1, the soft carrier particles have a target particle diameter ranging from 0.2 to 0.8mm, and a target form is a flat form and/or a cubic form.
Specifically, in the step S2, the mass percentage of the super-hard abrasive is 40-60%, and the mass percentage of the common abrasive is 40-60%, that is, the sum of the mass percentages of the super-hard abrasive and the common abrasive is 100%. The super-hard abrasive is selected from one or more of diamond, cubic boron nitride and the like; the common abrasive is selected from one or more of zirconia, silicon oxide, cerium oxide, silicon carbide, boron carbide, white corundum, brown corundum and the like.
Further, the particle size of the multicomponent abrasive is 0.1 to 4.0. Mu.m.
Specifically, in the step S3, the setting temperature of the heatable mixing device is 20 to 40 ℃ below the viscous flow transition temperature of the soft carrier particles, that is, the setting temperature is 20 to 40 ℃ lower than the viscous flow transition temperature of the soft carrier particles; stirring for 10-15min.
Further, in the step S4, when the soft carrier/hard abrasive composite particles are prepared, the multi-component abrasive is 10 to 25% by mass, and the soft carrier particles are 75 to 90% by mass, that is, the sum of the mass percentages of the multi-component abrasive and the soft carrier particles is 100%; stirring for 25-45min.
Specifically, in the step S5, the room temperature range is 25 +/-5 ℃, and the standing time is 4-6h. The soft elastic abrasive particles obtained have a target particle size in the range of 0.2 to 0.8mm and a target morphology of flat and/or cubic.
The invention also provides the soft elastic abrasive particles for tool polishing passivation, which are prepared by the preparation method. The soft elastic abrasive particles for tool polishing passivation processing comprise:
the soft carrier is made of a high-molecular viscoelastic material and has excellent elasticity; the main body of the soft elastic abrasive particles can elastically deform under the action of external force and is used for fixing, embedding and supporting hard abrasive materials;
the hard abrasive material consists of a common abrasive material and a superhard abrasive material; through the rotatory stirring effect of compounding device, make its sharp edges and corners pierce soft carrier, inlay on soft carrier surface to be used for the grinding to treat the processing work piece surface material.
The soft elastic abrasive particles of the present invention have excellent elasticity based on the unique viscoelasticity of the polymer-based soft carrier. The soft elastic abrasive particles are sprayed at a high speed through the spray gun and collide with the surface to be processed, the abrasive particles store certain elastic potential energy, and the stored potential energy is released after the abrasive particles slide with the surface of a workpiece to a certain degree, so that the soft elastic abrasive particles restore to the original shape and bounce from the surface to be processed at the same time, and finally two functions of passivation and polishing are realized. The hard abrasive is compactly embedded on the surface of the soft carrier, and can effectively participate in workpiece processing. The soft elastic abrasive particle processing cutter prepared by the invention has the advantages of low surface roughness, obvious arc of cutting edge, elimination of broken mouth, high surface quality and low subsurface damage after processing.
Compared with the prior art, the invention has the following beneficial effects:
1) The soft elastic abrasive particles have larger specific gravity and excellent elasticity, are matched with the conventional negative pressure suction-injection type sand blasting equipment in the field, are sucked by a spray gun to be mixed with air flow, are sprayed out by a nozzle through compressed air, can wipe, roll and plough the surface of a workpiece at a certain speed and pressure, and finely remove surface materials, so that the roughness of the processed surface is reduced;
2) The soft elastic abrasive particles are sharp in shape, have obvious edges and corners, are flat and cubic particles, so that under the condition that the overall emergent speed of the soft elastic abrasive particles is the same, the soft elastic abrasive particles can collide the surface of a workpiece by a smaller contact area, a single abrasive can generate larger pressure, the material removal amount is increased, the scratch is deepened, and the polishing passivation effect is more obvious;
3) According to the soft elastic abrasive grain, the soft carrier is subjected to micro viscous flow state-high elastic state-glass state transition to be embedded with the hard abrasive, so that the embedding effect between the soft carrier and the hard abrasive can be obviously enhanced, the integral service life of the soft elastic abrasive grain is prolonged, and the soft elastic abrasive grain can continuously work for 800 hours or more;
4) The soft elastic abrasive particles are simple in processing operation, high in processing efficiency and good in processing effect, can be used for processing 3D curved surfaces with complex shapes such as the surface of a cutter, a groove, a depression and a slit in place, and can uniformly passivate each position of the cutting edge of the cutter; the roughness Ra of the processed workpiece is less than or equal to 0.05 mu m, the arc size of the processed cutting edge is 5-12 mu m, the surface of the cutter has no scratch, and the technical index requirement of the cutter polishing passivation is completely met;
5) The soft elastic abrasive particles, the raw materials and the used manufacturing equipment have low cost, the preparation process is simple and stable, and the mass production, preparation and popularization are easy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts;
FIG. 1 is a schematic diagram of an embodiment of the process of the present invention;
FIG. 2 is a SEM illustration of soft elastic abrasive particles of the present invention;
FIG. 3 is a schematic view of the processing principle of the soft elastic abrasive particles of the present invention;
in the figure: 1. a spray gun; 2. processing the surface of a workpiece; 3. a surface grinding layer; 4. a soft carrier; 5. a hard abrasive;
FIG. 4 is a schematic front and rear view of a phi 8 bulk cemented carbide drill machined with soft elastic abrasive particles according to the present invention; in the figure: 1. a raw workpiece; 2. processing the workpiece;
fig. 5 is a SEM schematic view of the soft elastic abrasive particles of comparative example 1.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Unless otherwise specified, the raw materials used in the examples are all common commercial products that are directly available in the art. Room temperature refers to 25 ± 5 ℃.
Example 1
Thermoplastic polyurethane-based soft elastic abrasive particles with the particle size range of 0.4-0.8mm are prepared, the raw materials of the particles are made of Thermoplastic Polyurethane (TPU), boron carbide and diamond, and the mass percentage and the type of each raw material are detailed in table 1.
Table 1 mass percentage and type of each raw material
The preparation method of the soft elastic abrasive particles (see a process flow chart in figure 1) specifically comprises the following steps:
s1, processing a thermoplastic polyurethane substrate: and crushing the thermoplastic polyurethane master batch based on a freezing, crushing and granulating process. A freezing, crushing and granulating process is a conventional material processing mode in the field, and comprises the following specific processes: firstly, soaking thermoplastic polyurethane master batch in a liquid nitrogen environment at the temperature of 140 ℃ below zero for 5min, then sending the thermoplastic polyurethane master batch in a glass state into a crushing cavity of hammering type crushing equipment through a feeding rod, and collecting a product through processing. Then, the product passes through a No. 20 sieve, is supported by a No. 40 sieve, and collects the thermoplastic polyurethane particles in the interval of No. 40 to No. 20, namely collects the soft carrier thermoplastic polyurethane particles with the particle size range of 0.4 to 0.8mm and the shape of flat and cube;
s2, preparing a multi-component abrasive: putting 45g of boron carbide with the specification of W0.5 and 45g of diamond micro powder with the specification of M0/2 into a glass container, repeatedly stirring and mixing, sieving for 3 times by a No. 80 sieve, and collecting to obtain a uniformly dispersed multicomponent abrasive with the particle size range of 0.1-2.5 mu M;
s3, heating thermoplastic polyurethane particles: the thermoplastic polyurethane particles collected by 500g S1 are added into a mixing barrel with the diameter of 500mm and the height of 800mm, and the mixing barrel is placed in a heatable rotary mixer (which is conventional equipment in the field, mainly has heating and rotary mixing functions, and can be directly purchased, so the structure is not the innovation of the application, and is not repeated). Setting the temperature to 130 ℃ and stirring for 10min to obtain thermoplastic polyurethane particles with a certain degree of viscous flow transformation on the surface;
s4, preparing the thermoplastic polyurethane-based soft elastic abrasive particles: pouring the multi-component abrasive material obtained by 80g of S2 into the thermoplastic polyurethane particle system with the surface subjected to micro-viscous flow transformation obtained by S3. Continuously oscillating and stirring for 30min by a heatable rotary mixer to ensure that the hard grinding materials are compacted and uniformly distributed on the surface of the thermoplastic polyurethane, thus preparing the thermoplastic polyurethane-based composite particles with the hard grinding materials uniformly embedded on the surface;
s5, post-treatment of the thermoplastic polyurethane-based soft elastic abrasive particles: and collecting the product prepared in the S4 and standing for 5 hours at room temperature. And then, passing the product through a No. 20 screen, receiving the product by using a No. 40 screen, and collecting the thermoplastic polyurethane-based soft elastic abrasive particles in a No. 40-20 interval to obtain the thermoplastic polyurethane-based soft elastic abrasive particles with the particle size range of 0.4-0.8 mm.
Fig. 2 shows an SEM illustration of the soft elastic abrasive particles produced in this example. It can be seen from the figure that: the thermoplastic polyurethane-based soft elastic abrasive particles are sharp in shape, have obvious edges and corners and are cubic particles; and the soft elastic abrasive particles have a uniform particle size distribution, wherein the particle size is about 0.6mm.
FIG. 3 is a schematic view of the processing principle of the soft elastic abrasive particles of the present invention; in the figure: 1. a spray gun; 2. processing the surface of a workpiece; 3. a surface grinding layer; 4. a soft carrier; 5. a hard abrasive. Specifically, the soft elastic abrasive particles of the present invention are sucked by the spray gun 1 to be mixed with the air flow, and are sprayed out from the nozzle in the form of jet flow by compressed air, and the initial velocity reaches more than 80m/s, so that the soft elastic abrasive particles are accelerated and obtain kinetic energy. Then, the soft elastic abrasive particles reach the surface 2 of the workpiece to be processed, the soft elastic abrasive particles collide with the workpiece to cause deceleration, the soft elastic abrasive particles generate large compression based on the excellent elasticity of the soft elastic abrasive particles and stretch and roll along the surface of the workpiece, and the kinetic energy of the soft elastic abrasive particles is converted into elastic potential energy and stored. When the elastic potential energy is released, the soft elastic abrasive particles restore to the original shape and bounce from the surface of the workpiece at the same time, and then are separated from the surface of the workpiece. The soft elastic abrasive particles collide with the workpiece and are compressed, extended and bounced on the surface of the workpiece to generate scratching and plowing effects on the surface of the workpiece, so that materials on the surface of the workpiece are removed, and the purpose of passivation and polishing integrated processing is achieved.
The soft elastic abrasive particles prepared in this example were used in conjunction with conventional negative pressure suction-injection type sand blasting equipment in the field to perform a surface polishing experiment on a phi 8 cemented carbide drill. The adopted technological parameters are as follows: the sand blasting pressure is set to be 0.35MPa; the workpiece adopts a machining mode of forward and reverse rotation and up and down movement, and the rotating speed is set to be 30.0RPM; the spray angle of the spray gun is 45 degrees.
FIG. 4 is a schematic diagram showing the front and back of the soft elastic abrasive grain processing phi 8 cemented carbide drill prepared in the embodiment. By adopting the process parameters, when the number of times of forward and reverse rotation reaches 20 times, the total processing time is 5.5min, and the processing of the cutter can be completed. Detecting the surface of the machined cutter, wherein the surface roughness Ra is less than or equal to 0.05 mu m; the arc size range of the cutting edge reaches 0.005-0.012mm; the surface of the cutter has no scratch (see figure 4), and completely meets the technical index requirements of cutter polishing passivation.
Example 2
The natural rubber-based soft elastic abrasive particles with the particle size range of 0.2-0.4mm are prepared, the raw materials of the abrasive particles consist of Natural Rubber (NR), zirconia, ceria and diamond, and the mass percentage and the type of each raw material are detailed in table 2.
TABLE 2 quality percentage and type of each raw material
The preparation method of the soft elastic abrasive particles specifically comprises the following steps:
s1, processing a natural rubber base material: and crushing the natural rubber master batch based on a freezing, crushing and granulating process. A freezing, crushing and granulating process is a conventional material processing mode in the field, and comprises the following specific processes: firstly, natural rubber master batch is soaked in a liquid nitrogen environment at the temperature of 140 ℃ below zero for 5min, then the natural rubber master batch in a glass state is sent to a crushing cavity of hammering type crushing equipment through a feeding rod, and a product is collected through processing. Then, the product is screened by a No. 40 screen, and is supported by a No. 60 screen, and natural rubber particles within the interval of No. 60 to No. 40 are collected, namely soft carrier natural rubber particles with the particle size range of 0.2 to 0.4mm and the shape of flat and cubic are collected;
s2, preparing a multi-component abrasive: putting 40g of zirconium oxide with the specification of W3.5, 40g of cerium oxide with the specification of W3.5 and 55g of diamond micro powder with the specification of M1/2 into a glass container, repeatedly stirring and mixing, sieving for 3 times through a No. 80 sieve, and collecting to obtain a uniformly dispersed multi-component abrasive with the particle size range of 1.0-3.5 mu M;
s3, heating natural rubber particles: the natural rubber particles collected at 800g S1 were charged into a mixing bowl having a diameter of 500mm and a height of 800mm, and the mixing bowl was placed in a rotary mixer which was heated. Setting the temperature to 80 ℃ and stirring for 10min to obtain natural rubber particles with surfaces generating a certain degree of viscous flow transformation;
s4, preparing the natural rubber-based soft elastic abrasive particles: 120g of the multicomponent abrasive material obtained from the S2 is poured into the natural rubber particle system with the surface subjected to the micro viscous flow transformation obtained from the S3. Continuously oscillating and stirring for 40min by a heatable rotary mixer to compact and uniformly distribute the hard grinding materials on the surface of the natural rubber, thus preparing the natural rubber-based composite particles with the hard grinding materials uniformly embedded on the surface;
s5, post-treatment of the natural rubber-based soft elastic abrasive particles: and collecting the product prepared by S4 and standing for 4 hours at room temperature. And then, screening the product by a No. 40 screen, carrying by a No. 60 screen, and collecting the natural rubber-based soft elastic abrasive particles within the interval of No. 60 to No. 40 to obtain the natural rubber-based soft elastic abrasive particles with the particle size range of 0.2 to 0.4 mm.
The processing effect of the soft elastic abrasive particles obtained in example 2 was the same as that of example 1.
Example 3
The styrene thermoplastic elastomer-based soft elastic abrasive particles with the particle size range of 0.4-0.8mm are prepared, the raw materials of the particles are styrene thermoplastic elastomers, specifically styrene-butadiene-styrene block copolymers (SBS), green silicon carbide and cubic boron nitride, and the mass percentage and the type of each raw material are detailed in Table 3.
TABLE 3 weight percentages and types of the raw materials
The preparation method of the soft elastic abrasive particles specifically comprises the following steps:
s1, processing a styrene-butadiene-styrene block copolymer substrate: and crushing the styrene-butadiene-styrene block copolymer master batch based on a freezing crushing granulation process. A freezing, crushing and granulating process is a conventional material processing mode in the field, and comprises the following specific processes: firstly, soaking a styrene-butadiene-styrene block copolymer master batch in a liquid nitrogen environment at the temperature of-140 ℃ for 5min, then sending the styrene-butadiene-styrene block copolymer master batch in a glass state to a crushing cavity of hammering type crushing equipment through a feeding rod, and collecting a product through processing. Then, passing the product through a No. 20 screen, using a No. 40 screen to support, and collecting styrene-butadiene-styrene block copolymer particles within a No. 40-20 interval, namely collecting soft carrier styrene-butadiene-styrene block particles with the particle size range of 0.4-0.8mm and the shape of a flat or cube;
s2, preparing a multi-component abrasive: putting 175g of green silicon carbide micro powder with the specification of W2.5 and 255g of cubic boron nitride micro powder with the specification of M1/3 into a glass container, repeatedly stirring and mixing, sieving for 3 times by using an 80# sieve, and collecting to obtain a uniformly dispersed multi-component grinding material with the particle size range of 2.0-4.0 mu M;
s3, heating styrene-butadiene-styrene block copolymer particles: in a mixing bowl having a diameter of 800mm and a height of 1500mm, 2000g of the styrene-butadiene-styrene block copolymer particles collected in S1 were charged, and the mixing bowl was placed in a heatable rotary mixer. Setting the temperature to 120 ℃ and stirring for 15min to obtain styrene-butadiene-styrene segmented copolymer particles with surfaces generating a certain degree of viscous flow transformation;
s4, preparing the soft elastic abrasive particles based on the styrene-butadiene-styrene block copolymer: the multi-component abrasive obtained in step 420g of S2 was poured into the styrene-butadiene-styrene block copolymer particle system obtained in step S3, which had a surface undergoing a micro-viscous flow transition. Continuously oscillating and stirring for 40min by a heatable rotary mixer to compact and uniformly distribute the hard abrasive on the surface of the styrene-butadiene-styrene block copolymer to obtain styrene-butadiene-styrene block copolymer-based composite particles with the surfaces uniformly embedded with the hard abrasive;
s5, styrene-butadiene-styrene block copolymer-based soft elastic abrasive particle post-treatment: and collecting the product prepared in the S4 and standing for 6h at room temperature. And then, passing the product through a No. 20 screen, supporting the product by using a No. 40 screen, and collecting the styrene-butadiene-styrene block copolymer-based soft elastic abrasive particles within a range of No. 40 to No. 20 to obtain the styrene-butadiene-styrene block copolymer-based soft elastic abrasive particles with the particle size range of 0.4 to 0.8 mm.
The processing effect of the soft elastic abrasive particles obtained in example 3 was the same as that of example 1.
Comparative example 1
Comparative example 1 differs from example 1 in that: the soft carrier thermoplastic polyurethane particles of example 1, which had a flat or cubic shape, were replaced with soft carrier thermoplastic polyurethane particles having a rounded shape and no edges and corners. The preparation process is referred to example 1.
The SEM image of the resulting elastic abrasive particles prepared in this comparative example 1 is shown in fig. 5. As can be seen in fig. 5: the thermoplastic polyurethane-based elastic abrasive particles have rounded shapes and no obvious edges and corners.
Subsequently, the thermoplastic polyurethane-based elastic abrasive particles prepared in comparative example 1 were used in combination with a negative pressure suction-injection type sand blasting device to polish and passivate a phi 8 cemented carbide drill using the same processing parameters as those in example 1, and the processing effects are shown in table 4 below.
TABLE 4 polishing passivation effect of the products of example 1 and comparative example 1 on phi 8 bulk cemented carbide drills
As can be seen from table 4: the soft elastic abrasive particles (example 1) produced using the soft carrier thermoplastic polyurethane particles of the present invention, which are flat and cubic in shape, are significantly superior to the soft elastic abrasive particles (comparative example 1) produced using the soft carrier thermoplastic polyurethane particles of the present invention, which are rounded in shape and free of edges and corners, in the surface roughness and the arc size of the cutting edge of the workpiece to be machined, in the same machining process. Namely, the following results are shown: the soft elastic abrasive particles are sharp in shape, have obvious edges and corners, and are flat and cubic particles, so that under the condition that the overall emergent speed of the soft elastic abrasive particles is the same, the soft elastic abrasive particles can collide the surface of a workpiece with a smaller contact area, a single abrasive can generate larger pressure, the material removal amount is increased, scratches are deepened, and the polishing passivation effect is more obvious.
Comparative example 2
This comparative example differs from example 1 in that: a different preparation procedure was used than in example 1.
The method for making the resilient abrasive grain of this comparative example was: the elastic abrasive particles were made by atomizing an adhesive onto the surface of rolling soft carrier particles, then mixing the multicomponent abrasive with the adhesive-bonded soft carrier particles, and compacting the multicomponent abrasive on the surface of the soft carrier particles by centrifugal or impact force (comparative example 2).
Subsequently, the elastic abrasive particles prepared in comparative example 2 were used in combination with a negative pressure suction-injection type sand blasting device to polish and passivate a phi 8 cemented carbide drill using the same processing parameters as in example 1, and the processing effects are shown in table 5 below.
TABLE 5 Process effects of polishing passivation of a phi 8 cemented carbide drill using example 1 and comparative example 2
As can be seen from table 5: the elastic abrasive particles (comparative example 2) obtained by connecting the soft carrier and the hard abrasive using the adhesive as an intermediate medium had a processing effect equivalent to that of example 1 at the initial stage of processing. However, the processing effect of comparative example 2 gradually deteriorated with the increase of the continuous operation time period, and the soft elastic abrasive particles lost the processing ability after 300 to 500 hours of processing. Namely, the following results are shown: compared with the soft elastic abrasive particles prepared by using the atomized adhesive (comparative example 2), the soft elastic abrasive particles prepared based on the self-adhesion property of the high-molecular viscoelastic base material have stronger embedding effect between the soft carrier and the hard abrasive, so that the soft elastic abrasive particles have more excellent continuous processing effect and longer service life.
In conclusion, it can be seen that: the soft elastic abrasive particles with the core-shell-like structure are uniformly embedded on the surface of the soft carrier by the hard abrasive, when the soft elastic abrasive particles are applied to the polishing passivation processing treatment of the surface of the cutter, the soft carrier can deform when the abrasive particles collide with the surface of the cutter, so that the abrasive particles generate certain scratching, rolling and plowing effects on the surface of the cutter, the surface material is removed finely, and finally, the high-efficiency and high-precision polishing passivation integrated processing is realized. The soft elastic abrasive particles prepared by the invention can effectively solve the technical problems of low processing efficiency, poor precision, difficulty in integrated processing of polishing and passivation and uniform and stable quality in the existing tool surface treatment technology, greatly improves the processing efficiency and has high popularization value.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for preparing soft elastic abrasive particles for tool polishing passivation processing is characterized by comprising the following steps:
s1, processing of a high-molecular viscoelastic base material: crushing and screening the high-molecular viscoelastic base material master batch to obtain soft carrier particles with a target shape within a target particle size range;
s2, preparing a multi-component abrasive: mixing and screening a certain proportion of superhard abrasive and common abrasive to obtain uniformly dispersed multicomponent abrasive;
s3, heating soft carrier particles: stirring the soft carrier particles prepared in the step S1 at a certain temperature for a certain time to generate a certain degree of viscous flow transformation on the surface;
s4, preparing soft carrier/hard abrasive composite particles: uniformly pouring the multicomponent abrasive of S2 into the soft carrier particle system obtained in S3 according to a certain proportion, and continuously stirring to prepare soft carrier/hard abrasive composite particles;
s5, post-treatment of the soft carrier/hard abrasive composite particles: and (4) collecting the composite particles prepared in the step (S4), placing the composite particles in a room temperature environment for a certain time, and screening to obtain the composite particles.
2. The method for preparing the soft elastic abrasive particles for tool polishing and passivation according to claim 1, wherein in the step S1, the Shore hardness of the high-molecular viscoelastic base material master batch is less than or equal to 70HA, and the density of the high-molecular viscoelastic base material master batch is 0.6-2.2g/cm 3 (ii) a The high molecular viscoelastic base material master batch is specifically selected from one or more of natural rubber, isoprene rubber, polyurethane rubber, styrene thermoplastic elastomer, thermoplastic polyurethane, ethylene-vinyl acetate copolymer and polyolefin elastomer.
3. The method for preparing soft elastic abrasive particles for tool polishing and passivating according to claim 2, wherein in step S1, the soft carrier particles have a target particle size in the range of 0.2-0.8mm and a target morphology of flat and/or cubic shape.
4. The method for preparing the soft elastic abrasive particles for tool polishing and passivating according to claim 1, wherein in the step S2, the mass percentage of the super-hard abrasive is 40-60%, and the mass percentage of the common abrasive is 40-60%; the super-hard abrasive is selected from one or more of diamond and cubic boron nitride; the common abrasive is selected from one or more of zirconia, silicon oxide, cerium oxide, silicon carbide, boron carbide, white corundum and brown corundum.
5. The method for producing soft elastic abrasive particles for tool polishing and passivating according to claim 4, wherein the grain size of the multi-component abrasive is 0.1 to 4.0 μm.
6. The method for preparing the soft elastic abrasive particles for tool polishing and passivating according to claim 1, wherein in the step S3, the temperature is set to be 20-40 ℃ below the viscous flow transition temperature of the soft carrier particles; stirring for 10-15min.
7. The method for preparing soft elastic abrasive particles for tool polishing passivation according to claim 1, wherein in step S4, when preparing the soft carrier/hard abrasive composite particles, the multi-component abrasive is 10 to 25% by mass, and the soft carrier particles are 75 to 90% by mass.
8. The method for preparing soft elastic abrasive particles for tool polishing and passivating according to claim 1, wherein in the step S5, the room temperature is 25 ± 5 ℃ and the standing time is 4-6h.
9. Soft elastic abrasive particles for tool polishing and passivation manufactured by the manufacturing method according to any one of claims 1 to 8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211391321.XA CN115820209A (en) | 2022-11-08 | 2022-11-08 | Soft elastic abrasive particles applied to tool polishing passivation processing and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211391321.XA CN115820209A (en) | 2022-11-08 | 2022-11-08 | Soft elastic abrasive particles applied to tool polishing passivation processing and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115820209A true CN115820209A (en) | 2023-03-21 |
Family
ID=85527127
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211391321.XA Pending CN115820209A (en) | 2022-11-08 | 2022-11-08 | Soft elastic abrasive particles applied to tool polishing passivation processing and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115820209A (en) |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59227971A (en) * | 1983-06-09 | 1984-12-21 | Akebono Brake Ind Co Ltd | Wet abrasive |
JP2003011066A (en) * | 2000-07-25 | 2003-01-15 | Ebara Corp | Polishing tool and manufacturing method therefor |
US20050118939A1 (en) * | 2000-11-17 | 2005-06-02 | Duescher Wayne O. | Abrasive bead coated sheet and island articles |
CN1822921A (en) * | 2004-04-28 | 2006-08-23 | 株式会社东芝 | Polishing method for large-sized part and polishing particles used for the method |
CN1858135A (en) * | 2006-05-29 | 2006-11-08 | 李岳 | Elastic polishing particles |
CN101269479A (en) * | 2007-03-23 | 2008-09-24 | 株式会社不二制作所 | Substrate treatment method for portion to be coated |
CN101357525A (en) * | 2007-08-03 | 2009-02-04 | 株式会社不二制作所 | Method for producing metal mask for screen printing |
US20140329441A1 (en) * | 2011-12-21 | 2014-11-06 | Fuji Manufacturing Co., Ltd. | Method for producing elastic grinding material, elastic grinding material, and blasting method using said elastic grinding material |
CN104511844A (en) * | 2013-09-30 | 2015-04-15 | 株式会社不二制作所 | Method and device for manufacturing elastic abrasive method for blasting the elastic abrasive including method for recycling the elastic abrasive and device for blasting the elastic abrasive including device for recycling the elastic abrasive |
CN105778861A (en) * | 2014-12-24 | 2016-07-20 | 深圳富泰宏精密工业有限公司 | Elastic abrasive particle and manufacturing method thereof |
CN106030007A (en) * | 2013-12-23 | 2016-10-12 | 2-H化学有限公司 | Anti-slip flooring material, method for manufacturing anti-slip flooring material, and method for constructing floor by using anti-slip flooring material |
CN109880533A (en) * | 2019-03-26 | 2019-06-14 | 中南大学 | A kind of composite abrasive grain polishing solution and preparation method thereof |
US20190283212A1 (en) * | 2018-03-19 | 2019-09-19 | Fuji Manufacturing Co., Ltd. | Method for surface treatment of workpiece made from hard-brittle material |
CN112008609A (en) * | 2020-09-04 | 2020-12-01 | 深圳市鑫意晟科技有限公司 | Core-shell abrasive jet polishing method |
CN214723447U (en) * | 2021-03-05 | 2021-11-16 | 贺州学院 | Cutter polishing device integrating abrasive flow manufacturing and cutter polishing |
CN113652172A (en) * | 2021-09-17 | 2021-11-16 | 河南工业大学 | Elastic abrasive and preparation method thereof |
-
2022
- 2022-11-08 CN CN202211391321.XA patent/CN115820209A/en active Pending
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59227971A (en) * | 1983-06-09 | 1984-12-21 | Akebono Brake Ind Co Ltd | Wet abrasive |
JP2003011066A (en) * | 2000-07-25 | 2003-01-15 | Ebara Corp | Polishing tool and manufacturing method therefor |
US20050118939A1 (en) * | 2000-11-17 | 2005-06-02 | Duescher Wayne O. | Abrasive bead coated sheet and island articles |
CN1822921A (en) * | 2004-04-28 | 2006-08-23 | 株式会社东芝 | Polishing method for large-sized part and polishing particles used for the method |
CN1858135A (en) * | 2006-05-29 | 2006-11-08 | 李岳 | Elastic polishing particles |
CN101269479A (en) * | 2007-03-23 | 2008-09-24 | 株式会社不二制作所 | Substrate treatment method for portion to be coated |
CN101357525A (en) * | 2007-08-03 | 2009-02-04 | 株式会社不二制作所 | Method for producing metal mask for screen printing |
US20140329441A1 (en) * | 2011-12-21 | 2014-11-06 | Fuji Manufacturing Co., Ltd. | Method for producing elastic grinding material, elastic grinding material, and blasting method using said elastic grinding material |
CN104511844A (en) * | 2013-09-30 | 2015-04-15 | 株式会社不二制作所 | Method and device for manufacturing elastic abrasive method for blasting the elastic abrasive including method for recycling the elastic abrasive and device for blasting the elastic abrasive including device for recycling the elastic abrasive |
CN106030007A (en) * | 2013-12-23 | 2016-10-12 | 2-H化学有限公司 | Anti-slip flooring material, method for manufacturing anti-slip flooring material, and method for constructing floor by using anti-slip flooring material |
CN105778861A (en) * | 2014-12-24 | 2016-07-20 | 深圳富泰宏精密工业有限公司 | Elastic abrasive particle and manufacturing method thereof |
US20190283212A1 (en) * | 2018-03-19 | 2019-09-19 | Fuji Manufacturing Co., Ltd. | Method for surface treatment of workpiece made from hard-brittle material |
CN109880533A (en) * | 2019-03-26 | 2019-06-14 | 中南大学 | A kind of composite abrasive grain polishing solution and preparation method thereof |
CN112008609A (en) * | 2020-09-04 | 2020-12-01 | 深圳市鑫意晟科技有限公司 | Core-shell abrasive jet polishing method |
CN214723447U (en) * | 2021-03-05 | 2021-11-16 | 贺州学院 | Cutter polishing device integrating abrasive flow manufacturing and cutter polishing |
CN113652172A (en) * | 2021-09-17 | 2021-11-16 | 河南工业大学 | Elastic abrasive and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101925441B (en) | Plasma treated abrasive article and method of making same | |
BE1015215A3 (en) | Porous abrasive tool and method of making. | |
CN100402237C (en) | Abrasive tools for grinding electronic components | |
JP3795778B2 (en) | Resinoid grinding wheel using hydrogenated bisphenol A type epoxy resin | |
CN110387213B (en) | Method for manufacturing soft elastic abrasive, cutting tool and method for processing die | |
CN112059930A (en) | Grinding block for grinding disc for alloy material processing, preparation method of grinding block and grinding disc | |
CN102398229A (en) | Vitrified bond diamond wheel for grinding polycrystalline diamond cutter | |
JP2000507884A (en) | Rotary gravure process for the production of patterned polished surfaces | |
CN112536733B (en) | Ultra-precise grinding wheel and preparation method and application thereof | |
JPH09103965A (en) | Porous superbrasive grinding wheel and its manufacture | |
CN201998069U (en) | Composite-base diamond grinding disc | |
JPH10121113A (en) | Composite cutting blade and its production | |
CN113652172B (en) | Elastic abrasive and preparation method thereof | |
CN108838890B (en) | Diamond grinding wheel dressing method | |
CN115820209A (en) | Soft elastic abrasive particles applied to tool polishing passivation processing and preparation method thereof | |
CN202088116U (en) | Diamond grinding disc | |
CN1233987A (en) | Green honed cutting insert and method of making same | |
CN102066055B (en) | Self-bonded foamed abrasive articles and machining with such articles | |
CN108237442A (en) | A kind of processing technology of ultra-thin ceramic fingerprint recognition piece | |
CN111188198B (en) | Efficient wear-resistant polishing material and preparation method thereof | |
JPH11512657A (en) | Method and apparatus for forming knurls on a work piece, method for forming a product using the work piece, and the formed product | |
KR20040019821A (en) | Abrasive material and manufacturing method for abrasive material | |
CN205111464U (en) | Processing equipment of thick sapphire hemisphere of congruent , super hemisphere radome fairing | |
CN112476244A (en) | Superhard grinding tool dressing tool and preparation method thereof | |
CN2553956Y (en) | Grinding head structure for polishing ceramic concave-convex surface |
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 |