CN115213408A - Additive manufacturing process, additive layer, additive product and composite laser - Google Patents

Additive manufacturing process, additive layer, additive product and composite laser Download PDF

Info

Publication number
CN115213408A
CN115213408A CN202110432889.0A CN202110432889A CN115213408A CN 115213408 A CN115213408 A CN 115213408A CN 202110432889 A CN202110432889 A CN 202110432889A CN 115213408 A CN115213408 A CN 115213408A
Authority
CN
China
Prior art keywords
laser
additive
additive manufacturing
layer
powder
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
CN202110432889.0A
Other languages
Chinese (zh)
Inventor
龙俊耀
赵丽敏
王翘
韩金龙
牛增强
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.)
United Winners Laser Co Ltd
Original Assignee
United Winners Laser 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 United Winners Laser Co Ltd filed Critical United Winners Laser Co Ltd
Priority to CN202110432889.0A priority Critical patent/CN115213408A/en
Publication of CN115213408A publication Critical patent/CN115213408A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/105Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00Products made by additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00Coating starting from inorganic powder
    • C23C24/08Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106Coating with metal alloys or metal elements only
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01SDEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/005Optical devices external to the laser cavity, specially adapted for lasers, e.g. for homogenisation of the beam or for manipulating laser pulses, e.g. pulse shaping
    • H01S3/0071Beam steering, e.g. whereby a mirror outside the cavity is present to change the beam direction
    • 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

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention discloses an additive manufacturing process, an additive layer, a product after additive and a composite laser, and relates to the technical field of laser beam combination. The method comprises a pre-processing treatment process, an additive manufacturing processing treatment process and a post-processing treatment process. The invention solves the technical problems of high cost, great maintenance difficulty and poor equipment stability of the conventional laser of the ten-thousand watt level.

Description

Additive manufacturing process, additive layer, additive product and composite laser
Technical Field
The invention belongs to the technical field of laser additive manufacturing and laser repair, and particularly relates to a laser additive manufacturing process, an additive layer and a composite laser.
Technical Field
With the development of economic society, renewable energy sources are endowed with new missions such as energy conservation, emission reduction, greenhouse gas emission control, atmospheric pollution prevention and the like. Wind power and water power are used as new pollution-free and pollution-free power generation energy, great contribution is made to the power industry, abrasion repair of the aerospace field, the wind power, the water and electricity, a die, rail transit, a roller in the oil exploration field, the coal mining industry and the engineering machinery industry is mainly carried out by adopting common surfacing in the traditional method, and because the components are mainly made of high-carbon alloy steel or cast steel, the defects of large deformation, insufficient hardness, easy cracking and the like are caused to a workpiece by common surfacing, the use precision is seriously influenced, the quality of the produced product is reduced, and meanwhile, the service life of the workpiece is also shortened.
At present, because the production environment of some related manufacturing plants such as industry, energy, machinery and the like is severe, and the use load of industrial equipment parts is large, some metal parts with high additional value are corroded and abraded. In order to prolong the service life of production equipment, the appearance of the parts must be treated or repaired in advance, so laser cladding is one of the most important technologies for repairing metal surfaces.
In the power industry, power equipment is large in distribution quantity and runs uninterruptedly, and the damage probability of parts is high. The components of the power generation equipment bear the tests of fuel gas, high temperature, high pressure and corrosive medium to different degrees in the operating environment. In order to prolong the service life of expensive production equipment, the equipment used for a long time can be partially damaged due to aging, such as an impeller, a water turbine, a wheel shaft and the like in wind/hydraulic power generation equipment, the expensive production equipment can be repaired by using a surface remanufacturing technology, particularly blades used for a generator set are high in manufacturing cost, the repaired blades are reassembled and reused, and the power generation cost of a power plant is greatly reduced.
The laser additive manufacturing technology is an important method of a material surface modification technology and is an inexistent process, namely, a rapid solidification process for forming an alloy layer with completely different components and properties from a base material on the surface of the base material by rapidly melting alloy powder with different components and different properties and the surface of the base material by using the characteristic of high energy density of laser. Under the action of quick heat, the matrix is little affected by heat and has no deformation. The molten layer alloy self-forming system has compact structure, refined crystal grains, raised hardness and toughness and greatly improved surface performance. The laser additive manufacturing technology solves a series of technical problems of inevitable thermal deformation, thermal fatigue damage and the like in the traditional electric welding, argon arc welding and other hot processing processes.
In the prior art, laser additive manufacturing technology is to melt powder and a matrix by laser beam irradiation, so that the thin layer on the surface of the melt powder and the matrix is rapidly melted and rapidly solidified to form a metallurgically bonded surface coating, thereby improving the performances of wear resistance, heat resistance, corrosion resistance and the like of the matrix surface. However, the conventional laser cladding repair technology is adopted to repair the workpieces such as wind power, water and electricity, dies, rollers and the like, and the high-hardness, high-thickness and large-area laser cladding repair of the coating required by the workpiece to be repaired has high requirements on the selection of powder materials and the specific process.
In the existing laser additive manufacturing technology, a single optical fiber additive manufacturing technology is adopted at present, namely, one optical fiber is used for additive manufacturing, the single optical fiber technology only can be used for partial products at present, and partial products cannot be repaired by the single optical fiber, for example, the absorptivity of copper materials, copper bars or copper alloy materials to laser is extremely low, and the absorptivity of copper to a conventional optical fiber laser in an infrared band of 1060 is lower than 15%, so that the single optical fiber is used for additive manufacturing of the copper materials or the copper alloy, the laser needs to use a laser in the ten-kilowatt level, and the laser in the ten-kilowatt level at present is high in cost, extremely high in maintenance difficulty and poor in equipment stability.
Disclosure of Invention
In view of this, the present invention provides a laser additive manufacturing process, an additive layer and a composite laser, which are aimed at overcoming the defects existing in the prior art.
A multi-wavelength blue laser composite additive manufacturing process comprises a processing pretreatment process, an additive manufacturing processing process and a processing post-treatment process.
Optionally, the pretreatment process includes:
step S10: and carrying out flaw detection and surface cleaning treatment on the surface of the workpiece needing to be subjected to additive manufacturing.
Optionally, the additive manufacturing processing process includes:
step S20: the description process is suitable for additive manufacturing of pure copper powder and copper material, and also supports additive manufacturing of iron-based powder, nickel-based powder, cobalt-based powder or ceramic powder and copper or other alloy materials, and uses copper powder to perform additive manufacturing on damaged and missing parts for repairing and leveling, wherein the laser beam is single blue laser or composite laser of blue laser and semiconductor laser;
step S30: scanning the surface of a workpiece to be repaired by adding materials with laser beams, and synchronously adding a strengthening powder material to form a strengthening layer on the surface of the workpiece, wherein the laser beams are single blue lasers or compound lasers of the blue lasers and semiconductor lasers.
Optionally, when the laser beam is a single blue laser:
the wavelength of the blue laser is 430-470 nm;
the power of the blue laser is more than or equal to 1000w;
the core diameter of the blue laser is 800um;
the spot size of the blue laser is 4mm.
Optionally, when the laser beam is a composite laser of a blue laser and a semiconductor laser:
the wavelength of the blue laser is 430-470 nm;
the power of the blue laser is more than or equal to 1000w;
the core diameter of the blue laser is 800um;
the wavelength of the semiconductor optical fiber laser is 890-990 nm;
the power of the semiconductor optical fiber laser is more than or equal to 3000w;
the core diameter of the semiconductor fiber laser is =600um;
the size of the light spot of the multi-wavelength composite laser after being compounded can reach 4mm;
the thickness of the additive manufacturing can reach 0.1-5.0 mm;
the copper base material is copper, the thickness of the copper base material is more than or equal to 2mm;
the absorption rate of the blue laser to copper and copper alloy is 65 percent higher, and the comprehensive absorption rate of the laser after compounding is more than or equal to 85 percent;
the composite laser is laser coaxially output by a semiconductor laser and a blue laser.
Optionally, the post-processing treatment process includes:
step S40: and (5) material reducing forming processing and crack detection.
Optionally, the pretreatment process further includes:
step S50: the surface treatment of the workpiece needing the additive comprises the steps of removing a fatigue layer on the surface of the workpiece, and removing grinding fluid stuck to the surface by using alcohol after the removal.
Optionally, the pretreatment process further includes:
step S60: the pre-processing treatment also comprises annealing the workpiece, so that the hardness of the 0.5mm position of the surface of the workpiece is reduced to HRC40-HRC45.
Optionally, the pretreatment process further includes:
step S70: preheating the copper bar and preserving heat for 4 hours at the preheating temperature of 200 ℃.
Optionally, the post-processing treatment process further includes:
step S80: and (3) stress relief annealing heat treatment, wherein the stress relief annealing heat treatment is to enlarge light spots in a mode of increasing defocusing amount to achieve a laser quenching effect and rapidly scan and remelt a laser additive manufacturing layer to eliminate surface thermal stress when the surface temperature of the workpiece is not reduced after laser additive manufacturing and processing.
An additive layer, which may comprise one or more layers, may be obtained by the above process steps.
Optionally, when the additive layer comprises three layers, the three layers may be a tie layer, a reinforcing layer, and a skin layer;
the bonding layer: the iron-based powder comprises 0.4-0.8 wt% of C, 4.0-6.0 wt% of Cr, 1.3-1.7 wt% of B, 2.5-3.5 wt% of Si, 28-32 wt% of Ni and the balance of Cu;
the addition of C and Si can improve the strength of the metallurgical bonding layer and the wear resistance of the additive manufacturing layer, and the effect of transition layers among the bonding layers is also realized, so that the generation of cracks or the tendency of cracks in additive manufacturing is reduced.
The strengthening material in the strengthening layer comprises the following components in percentage by weight of less than or equal to 0.1 percent of C, cr:17-19%, B:1.5-2.5%, si:1.5-2.5%, ni:8-10%, mo:1-1.5%, V:0.5-1.5% and the balance of Cu.
The name of the surface layer powder is CuCrZr and the proportion is as follows: 0.75% of Cr, 0.077% of Zr, and the balance of Cu, the specification is 15-53um, and the particle size is as follows: d10:20.5um, D50:33.6.5um, D90.
Optionally, the thickness of the additive layer is 0.1-5.0 mm or more than or equal to 2mm.
The surface of the additive product is attached with any additive layer, or the additive product can be obtained through any additive manufacturing process, or the additive product is obtained through any additive manufacturing process, or the surface of the additive product is attached with the additive layer, wherein the product to be additively manufactured can be an automobile hot forming die made of Cr12 material, and the surface of the automobile hot forming die made of the additive Cr12 material is provided with the additive layer for improving the heat resistance, impact resistance and abrasion resistance of the die.
The laser beam output by the composite laser can be applied to the additive manufacturing process, the process of obtaining an additive layer, the any multi-wavelength blue-light laser composite additive manufacturing process to obtain any additive layer, and the any multi-wavelength blue-light laser composite additive manufacturing process to obtain the additive product. .
The beneficial effects of the invention are as follows: the laser additive manufacturing process provided by the invention has good controllability and is easy to realize automatic control, the additive manufacturing layer and the substrate layer have no coarse casting structure, the additive manufacturing layer and the interface structure thereof are compact, crystals are fine, and the defects of holes, impurities, cracks and the like do not exist, so that the loss of workpieces can be effectively repaired, and the performances of wear resistance, corrosion resistance, heat resistance, oxidation resistance and the like of the surface of the substrate material are improved.
Drawings
Fig. 1 is a schematic flow diagram of a multi-wavelength composite additive manufacturing method according to an embodiment of the invention;
FIG. 2 is a schematic diagram showing the absorption rates of seven metals, namely aluminum Al, copper Cu, gold Au, silver Ag, titanium Ti, nickel Ni and stainless steel 304 (SS 304), at normal temperature corresponding to different laser wavelengths;
fig. 3 is a schematic view of an optical composition structure of a related art employing a semiconductor laser and a blue laser;
FIG. 4 is a schematic illustration of blue laser + semiconductor fiber laser additive manufacturing powder and beam focus in accordance with the present invention;
FIG. 5 is a schematic diagram of the absorption and reflection process of laser light on the surface of a material;
FIG. 6 is a schematic illustration of additive manufacturing powders;
FIG. 7 is a metallographic representation of a metallurgical bonding layer after laser additive manufacturing;
fig. 8 is a schematic view of a laser additive manufactured three layer metallurgical bond coat structure.
Detailed description of the preferred embodiments
In order to make the content of the present invention more clear, concise and practical, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, various technical solutions involved in specific embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Referring to fig. 1-8, example 1:
in recent years, with the rapid development of automobile manufacturing industry in China, the automobile mold industry in China also develops rapidly, but compared with the advanced level of automobile mold manufacturing in China, the automobile mold manufacturing method has obvious gap. Because the requirements of automobile mould manufacture on technical requirements and product quality are higher and higher, the mould has poor precision, short service life and long development period and is a hard damage of the automobile mould manufacture. In the using process, the mould is abraded in different degrees, the rejection rate of the mould reaches 30 percent due to wrong processing, and huge waste is caused.
By adopting the process, the thin layer on the surface of the matrix is simultaneously melted by laser irradiation, and the coating which has extremely low dilution and is metallurgically bonded with the matrix metal is formed after the coating is rapidly solidified, so that the performances of wear resistance, corrosion resistance, heat resistance, oxidation resistance and the like of the surface of the matrix material are obviously improved.
The additive manufacturing method is used for the automobile hot forming die made of the Cr12 material and comprises the following steps:
the first step is as follows: pretreatment of additive manufacturing, namely cleaning visible oil stains, oxidation layers and residues on the surface of a die by using laser cleaning or removing the visible oil stains and residues on the surface by using a cleaning agent; generally, the surface of the mold is heated at a low temperature of 100 ℃ to remove moisture, oil and other impurities permeating into the shallow layer of the surface of the mold.
The second step: surface detection, which is to detect surface cracks and damages by using a dye check method; the specific operation is as follows: detecting and recording original use conditions, hardness and mechanical property parameters of the die; recording the service life of the die to be reinforced, the material of the substrate, the working state and the original heat treatment state; detecting whether the part needing strengthening has defects such as cracks, casting defects, sand holes and the like by methods such as coloring, ultrasonic or X-ray; and detecting the sizes of all parts of the die, and determining the worn part and the missing size.
The third step: and (3) pretreating the surface of the die, removing the fatigue layer of the die by grinding and cutting or machining, grinding the cracks and the missing part into regular grooves until the cracks disappear, and cleaning.
The fourth step: repairing the wound, scanning along the groove direction by laser, adding iron-based powder for remanufacturing at the same time, melting the powder and a small amount of matrix, and filling the gap and the matrix; the edge edges are well protected by a three-line edge covering method. The alloy powder consists of C0.4-0.8 wt%, cr 4.0-6.0 wt%, B1.3-1.7 wt%, si 2.5-3.5 wt%, ni 28-32 wt% and Fe for the rest. (semiconductor laser power P =1600W, blue laser power set to 0W, i.e. used for additive manufacturing with the semiconductor laser inside the multi-wavelength composite laser.
It is noted that the powder has a C content of 0.4-0.8% and improved yield point and tensile strength rise at the repaired site. Meanwhile, a proper amount of B and Si are added to be used as a reducing agent and a deoxidizing agent in the cladding process, so that the elastic limit, the yield point and the tensile strength of a cladding layer are improved, and a matrix mainly comprising austenite is formed after the cladding layer is solidified.
The fifth step: manufacturing an integral over-tolerance ruler strengthening layer, planning a remanufacturing running track to be matched with the shape of the surface of a mould by using a manipulator to teach and program, scanning the surface of the mould by laser, and simultaneously adding a strengthening material for remanufacturing (the laser power of a semiconductor is P =2000, the laser power of a blue laser is =0W, and the scanning speed is V =1000 mm/min) by a synchronous airborne powder feeder, so that the surface of the mould is provided with a laser preparation strengthening layer, and the heat resistance, impact resistance and wear resistance effects of the mould are improved;
the adopted alloy powder comprises the following components in percentage by weight of less than or equal to 0.09 percent of C, cr:20-40%, B:0.5-1.5%, si:1.5-2.5%, ni:5-8%, mo:1.5-5.5%, V:0.5-1.0 percent, and the balance of Fe.
The adopted manipulator can be an ABB-IRB6700-1500 six-axis manipulator (the action range is 0.35M-3.2M, the repetition precision is 0.05 mm), and the laser can be a UW3000W semiconductor laser which is independently developed and developed by the home and a 1000W blue laser which is independently developed and developed by the home.
Controlling the content of C to be less than or equal to 0.1% is beneficial to improving the wettability of the additive manufacturing layer and preventing cracks and air holes from being generated in the additive manufacturing process. The Cr content is increased, a proper amount of Mo is added to perform basic alloying strengthening on the iron-based powder, the additive manufacturing layer can reach more than 50HRC even if the carbon content is reduced, the requirements of the die are fully met, and the wear-resistant anticorrosive effect is high.
And a sixth step: after additive manufacturing, the additive manufactured layer is inspected. And (3) detecting the hardness of the surface layer of the additive manufacturing by using a hardness tester, detecting whether the reinforced layer and the combined layer have defects such as air holes, slag inclusion, cracks and the like which influence the mechanical properties of the die by using X-ray, and checking whether the quality is qualified.
The invention adopts the multi-wavelength composite laser additive manufacturing technology to process under the condition of keeping the matrix hardness HR30-40 of the die unchanged, so that the surface strength of the die can reach HRC58-62, the laser processing and the mechanical processing are combined, the addition and the subtraction are combined, the homogenization and the local strengthening (functional surface) are combined, and the service performance of the product after the additive manufacturing is even superior to that of the product manufactured by the original design.
Referring to fig. 1-8, example 2:
the following examples are further illustrative and supplementary to the present invention and do not limit the present invention in any way.
As shown in fig. 1, the present invention provides a multi-wavelength additive manufacturing method, comprising:
s101, cleaning the surface of a workpiece material needing material increase, and using a flaw detection developer to check whether cracks exist on the surface of the workpiece or not after the cleaning;
s102, cutting the fatigue layer on the surface of the processed workpiece by using a milling machine, milling the fatigue layer to a thickness of 0.8mm, and cleaning the surface of the workpiece again after the fatigue layer is processed;
s103, performing laser red light confirmation and focus finding on the composite laser
After the normal red light is confirmed, the test can be started to determine whether the laser can be normally emitted. The blue portion and the semiconductor portion are tested separately while the laser is in a high voltage state.
The laser test adopts a pulse mode, namely spot welding.
When inspecting the blue portion, the procedure was as follows:
(1) with the waveform # 0, a power of 100W, pulse width of 20ms,
and setting the power 0W and the pulse width 0ms on the semiconductor page, namely, emitting light by only blue light.
(2) A small stainless steel plate is placed below the laser head, and the position and the height of the laser head are adjusted to enable red light to be located on the small steel plate and enable the diameter of the red light to be at the minimum value.
(3) Triggering light emission and observing whether the CCD image flashes or not and whether a welding spot is formed on the steel plate or not.
When detecting the semiconductor part, the steps are as follows:
(1) with the waveform No. 1, the power 0W and the pulse width 0ms are set on the data page of the blue light waveform,
the power 300W and the pulse width 20ms are set on the semiconductor page, namely the single semiconductor emits light.
(2) The procedure was the same as when examining the blue portion.
(3) The procedure was the same as when examining the blue portion.
The Z-axis numerical value is adjusted by using the method to perform dotting once on the small steel plate every 1mm of light emission, the light spot at a certain Z-axis coordinate is found to be the minimum, the dotting sound is the loudest, and the maximum spark position is the focus;
s104, mounting and positioning parts according to the workpiece, mounting the copper roller on a positioner of an external shaft by using a crown block, fixing the copper roller by using a three-jaw chuck, wherein the three-jaw chuck and the copper roller need to be concentric, supporting and positioning the other side of the copper roller by using a top, and a thimble also needs to be concentric with the copper roller and the three-jaw chuck;
s105, determining the defocusing amount and the powder focus, wherein a positive defocusing amount of 3mm is used as an additive surface, powder is fed in a coaxial powder feeding mode, and the powder focus and the laser beam focus are on the same plane;
s106, additive track setting, namely editing the track of the copper roller needing additive by using a robot.
S107, setting process parameters: the power of a blue laser is 1000W, the power of a semiconductor laser is 2600W, the defocusing amount is 3mm, the rotating and moving speed of a positioner is 50mm/s, powder is coaxially fed in four ways, the powder feeding amount is 1 r/min, the powder feeding repeatability is up to +2%, and various coating powders with the particle diameter of 900-90 mu m can be conveyed. The setting range of the powder feeding disc speed is 0.00-50.00 (g/min), and the powder feeding speed is continuously adjustable; argon gas is 8L/Min;
serial number Actual value (rpm/rev) Powder delivery (g/min)
1 0.5 11.0
2 0.6 13.9
3 0.7 16.3
4 0.8 18.6
5 0.9 21.0
6 1.0 23.5
7 1.1 26.8
8 1.2 29.2
9 1.3 31.7
10 1.4 34.6
11 1.5 37.1
12 1.6 39.9
13 1.7 42.5
14 1.8 44.7
15 1.9 47.2
16 2.0 49.2
S108, outputting blue laser to the surface of the copper roller and the surface of copper powder through a laser so as to enable the powder and the surface of the copper roller to form a liquid molten pool surface;
s109, outputting semiconductor laser through a laser to act on the surface of the liquid molten pool, so that the semiconductor fiber laser is absorbed on the surface of the liquid molten pool to form a complete molten state, and the powder and the copper roller form metallurgical bonding;
s110, driving a laser emitting unit arranged on the robot to move through an external positioner to form a material increase manufacturing track, finally forming a finished metallurgical bonding layer on the surface of the powder and the surface of the copper roller, wherein the thickness of a single layer can be increased by 1.5-2 mm, adjusting the powder feeding amount according to requirements, and performing material increase manufacturing, wherein the thickness of the material increase is 3mm.
S111, performing laser stress relief annealing after material increase by using a large light spot with semiconductor power of 3000W, blue laser power of 1000W and defocusing amount of 50mm, and performing heat preservation for 24 hours by using heat preservation cotton when the material increase temperature reaches about 200 ℃;
and S112, observing and detecting the surface after the material is added. Observing whether cracks exist on the surface after material addition by using a magnifying lens, and detecting whether microcracks exist by using a flaw detector and a developer;
s113, material reduction and forming, namely processing the additive rough layer on the surface by using a milling machine, and downwards milling the rough layer on the surface by using the milling machine for 0.3mm to ensure that the surface is bright and beautiful;
s114, cleaning the surface again, and detecting whether pores and microcracks exist;
s115, calibrating the hardness of the surface additive layer by using a hardness tester, measuring the hardness to be 55HRC according to actual requirements, and blending the hardness according to the hardness of powder;
s116, powder preparation
First layer bonding layer: the copper alloy powder material comprises, by weight, 0.4-0.8% of C, 4.0-6.0% of Cr, 1.3-1.7% of B, 2.5-3.5% of Si, 28-32% of Ni and the balance of Cu.
The strengthening material of the second strengthening layer comprises the following components in percentage by weight of less than or equal to 0.1 percent of C, cr:17-19%, B:1.5-2.5%, si:1.5-2.5%, ni:8-10%, mo:1-1.5%, V:0.5-1.5% and the balance of Cu.
A third surface layer: copper alloy powder CuCrZr and the proportion: 0.75 percent of Cr, 0.077 percent of Zr, and the balance of Cu, the specification is 15-53um, and the particle size is as follows: d10:20.5um, D50:33.6.5um, D90;
the manufacturing process of the multi-wavelength composite additive comprises the following steps:
serial number P1 P2 V SFL PYL DW H CS
1 1000 1000 600 34 1.2 2 1 1
2 1000 1000 300 25 1.2 2 1.4 1
3 1000 1000 360 25 1.2 2 1.5 1
4 1000 1000 720 22 1.2 2 1.1 1
5 1000 800 720 15 1.2 2 0.4 1
6 1500 1000 1500 30 1.2 2 0.8 1
7 2000 1000 1800 30 1.2 2 1 1
8 2500 1000 1800 30 1.2 2 1.3 1
9 2500 800 1500 30 1.2 2 1.5 1
10 2500 1000 1200 30 1.2 2 1.2 1
P1, semiconductor laser power KW; power KW of blue laser P2: v: the speed is mm/min; SFL, powder feeding amount g/min; PYL is offset mm; DW: the effective lap joint width is mm; h: the thickness is mm; CS: number of layers.
First layer bond layer parameter selection: the power of a semiconductor is 1000, the power is 800W, the powder feeding quantity is 15 at the speed of 720mm/min, the deviation is 1.2mm, the effective width is 2mm, and the thickness of a bonding layer is 0.4mm;
selecting process parameters of the second layer of the strengthening layer: the semiconductor power is 2500, the power is 1000W, the speed is 1200mm/min, the powder feeding amount is 30, the deviation is 1.2mm, the effective width is 2mm, and the thickness of a bonding layer is 1.2mm;
selecting process parameters of the third surface layer: the semiconductor power is 1500, the power is 1000W, the speed is 1500mm/min, the powder feeding amount is 30, the deviation is 1.2mm, the effective width is 2mm, and the thickness of the bonding layer is 0.8mm;
performing replica processing;
and grinding the additive manufacturing surface layer to a required size by adopting a numerical control milling machine.
Surface flaw detection;
and (3) flaw detection is carried out on the surface of the additive manufacturing by adopting a flaw detection agent, the surface of the machined and molded copper roller is detected, and whether air holes, cracks and the like exist or not is detected.
According to the invention, a cladding layer with a higher thickness is obtained by adopting a multi-wavelength composite laser additive manufacturing technology, the defects of the coating are few, and the coating has excellent mechanical properties, so that the recycling of a copper roller to be scrapped or a copper bar and a copper material is realized, and the laser additive manufacturing technology is widely applied to the repairing of copper and copper alloy.
And adopting a laser surface annealing process to reduce the hardness of the copper roller surface within the thickness range of 1.5mm to 45HRC. The hardness of the cladding layer on the surface is 65HRC, so that a 1mm combined strengthening layer of the copper roller substrate is formed. The high-hardness substrate can provide strong supporting force for the surface composite layer to respond to the strong stress on the surface. The surface annealing layer has good toughness to deal with elastic stress and can permeate strong pressure stress into the hard body to be digested and removed.
Compared with argon arc welding, the surface of the base material is only slightly melted in the laser processing process, and the thickness of the slightly melted layer is 0.05-0.1mm. The heat affected zone of the matrix is extremely small, generally 0.1-0.2mm. As shown in fig. 1, the schematic diagram of the laser cladding heat affected zone is about one tenth of that of argon arc welding.
In addition, the laser additive manufacturing layer and the substrate are in metallurgical bonding, and the bonding strength is not lower than 90% of that of the original substrate material. The temperature rise of the matrix in the laser processing process is not more than 80 ℃, and the matrix basically has no deformation after laser processing.
And the laser additive manufacturing technology has good controllability and is easy to realize automatic control. The cladding layer and the substrate have no coarse casting structure, the cladding layer and the interface structure thereof are compact, the crystal is fine, and the defects of holes, impurities, cracks and the like are avoided.
The invention provides a multi-wavelength composite additive manufacturing method, which comprises the steps of firstly, carrying out beam integration on a blue laser and a semiconductor laser, then coaxially outputting laser, outputting blue laser to the surface of a copper roller through the blue laser, and irradiating the blue laser on the surfaces of copper powder and the copper roller. However, the depth of the molten state is shallow, so that the copper powder and the copper roller can not be in a complete molten state, and the copper powder and the copper roller can not be effectively connected in a metallurgical bonding mode. And then, outputting semiconductor laser through a semiconductor laser to act on the surface of the incomplete melting liquid molten pool so as to enable the surface of the incomplete melting liquid molten pool to absorb the energy of the semiconductor laser to form a liquid state in a complete melting state, adding a beam of semiconductor fiber laser with high power density to act on the surface of the liquid molten pool, wherein the absorption rate of the liquid molten pool to the semiconductor fiber laser is increased to about 20% from about 2% of the solid state, the comprehensive absorption rate of copper powder and a copper roller to the laser can reach more than 85%, and the copper powder and the copper roller can form a metallurgical bonding layer with effective depth only by increasing the power of the fiber, so that the depth and the stability of the molten pool are increased. Due to the fact that the low power of the optical fiber of the blue-off laser plays a role in preheating absorption, excessive boiling of a molten pool is avoided, and splashing is effectively restrained. And then, a sixth shaft of the robot drives a laser emitting unit of the laser to move to form a welding track, the sixth shaft of the robot drives the laser emitting unit to move from a starting point of the welding track to a terminal point of the track, along with the movement of the laser beam, the material and the powder in the front of the moving direction begin to melt, a molten pool at the rear begins to cool and solidify, a stable metallurgical bonding layer is formed after solidification, and finally a complete material increase surface layer is formed, so that the copper powder and the copper material are effectively bonded together.
The laser additive manufacturing method adopts the additive manufacturing mode of blue laser and semiconductor laser, so that the utilization rate of the whole laser is higher, the power of the whole laser can reach 4KW (the semiconductor is more than or equal to 3KW, and the blue light is more than or equal to 1 KW), the comprehensive absorption rate of the material to the laser can reach about 80 percent, the laser additive manufacturing application of the copper material can be completed by utilizing lower total power, the process is stable, the problem of insufficient bonding layer strength insufficient rosin joint can not occur easily, no splashing is generated in the additive manufacturing process, the additive width can be adjusted, the powder utilization rate can reach 95 percent, and the product performance of additive manufacturing is greatly improved.
In the embodiment provided by the invention, preferably, the laser emitting unit can simultaneously output the semiconductor fiber laser and the blue laser, and the semiconductor fiber laser and the blue laser are output coaxially.
In the technical scheme, the laser emitting unit is connected with the laser and focuses the laser to perform the material increase function, the laser emitting unit needs to simultaneously meet the output of semiconductor fiber laser and blue laser, the output mode is coaxial output, the blue laser and the semiconductor laser can be used independently, and the blue laser and the semiconductor laser can also be used in a composite mode.
In the embodiment provided by the invention, preferably, the blue laser outputs blue laser until the liquid molten pool formed on the surfaces of the copper powder and the copper substrate is a non-completely molten liquid molten pool, and then the semiconductor laser outputs high-energy laser to change the non-completely molten liquid into a completely molten liquid molten pool, so that the powder and the substrate form an effective metallurgical bonding layer, and the utilization rate and the production efficiency of the laser are improved.
The wavelength of the blue laser is 430-470 nm.
The power of the blue laser is more than or equal to 1000w.
The core diameter of the blue laser is 800um.
The wavelength of the semiconductor optical fiber laser is 890-990 nm.
The power of the semiconductor optical fiber laser is more than or equal to 3000w.
The core diameter of the semiconductor fiber laser is =600um.
The size of the light spot of the multi-wavelength composite laser after being compounded can reach 4mm.
The thickness of the additive manufacturing can reach 0.1-5.0 mm.
The copper base material is copper, the thickness of the copper base material is more than or equal to 2mm.
The absorption rate of the blue laser to copper and copper alloy is 65 percent, and the comprehensive absorption rate of the laser after compounding is more than or equal to 85 percent.
The compound laser is a semiconductor laser and a blue laser which coaxially emit light.
The composite laser can be used separately or simultaneously, and the semiconductor laser can be used separately when additive manufacturing is carried out on non-copper and copper alloy products.
While the invention has been described with reference to the above embodiments, the scope of the invention is not limited thereto, and the above components may be replaced with similar or equivalent elements known to those skilled in the art without departing from the spirit of the invention.

Claims (18)

1. An additive manufacturing process is characterized by comprising a pre-processing process, an additive manufacturing processing process and a post-processing process.
2. The additive manufacturing process of claim 1, wherein the pre-process treatment process comprises:
step S10: and carrying out flaw detection and surface cleaning treatment on the surface of the workpiece needing to be subjected to additive manufacturing.
3. The additive manufacturing process of claim 2, wherein the additive manufacturing process comprises:
step S20: the description process is suitable for additive manufacturing of pure copper powder and copper material, and simultaneously supports additive manufacturing of iron-based powder, nickel-based powder, cobalt-based powder or ceramic powder and copper or other alloy materials, and uses copper powder to perform additive manufacturing on damaged and missing parts for repairing and leveling, wherein the laser beam is single blue laser or composite laser of blue laser and semiconductor laser;
step S30: scanning the surface of a workpiece to be repaired by adding materials with laser beams, and synchronously adding a strengthening powder material to form a strengthening layer on the surface of the workpiece, wherein the laser beams are single blue lasers or compound lasers of the blue lasers and semiconductor lasers.
4. The additive manufacturing process of claim 3, wherein when the laser beam is a single blue laser:
the wavelength of the blue laser is 430-470 nm;
the power of the blue laser is more than or equal to 1000w;
the core diameter of the blue laser is 800um;
the spot size of the blue laser is 4mm.
5. The additive manufacturing process of claim 4, wherein when the laser beam is a composite laser of a blue laser and a semiconductor laser:
the wavelength of the blue laser is 430-470 nm;
the power of the blue laser is more than or equal to 1000w;
the core diameter of the blue laser is 800um;
the wavelength of the semiconductor optical fiber laser is 890-990 nm;
the power of the semiconductor optical fiber laser is more than or equal to 3000w;
the core diameter of the semiconductor fiber laser is =600um;
the size of the light spot of the multi-wavelength composite laser after being compounded can reach 4mm;
the composite laser is laser coaxially output by a semiconductor laser and a blue laser.
6. The additive manufacturing process of claim 3, wherein the post-process treatment process comprises:
step S40: and (5) material reduction forming processing and crack detection.
7. The additive manufacturing process of claim 6, wherein the pre-process treatment process further comprises:
step S50: the surface treatment of the workpiece needing the additive comprises the steps of removing a fatigue layer on the surface of the workpiece, and removing the grinding fluid stuck to the surface by using alcohol after the removal.
8. The additive manufacturing process of claim 7, wherein the pre-process treatment process further comprises:
step S60: the pre-processing treatment also comprises annealing the workpiece to reduce the hardness of the 0.5mm position of the surface of the workpiece to HRC40-HRC45.
9. The additive manufacturing process of claim 8, wherein the pre-process treatment process further comprises:
step S70: and (4) preheating the copper bar and preserving heat for 4 hours at the preheating temperature of 200 ℃.
10. The additive manufacturing process of claim 9, wherein the post-process treatment process further comprises:
step S80: and (3) stress relief annealing heat treatment, wherein the stress relief annealing heat treatment is to enlarge light spots in a defocusing amount increasing mode to achieve laser quenching effect fast scanning remelting laser additive manufacturing layer to eliminate surface thermal stress when the surface temperature of the workpiece is not reduced after laser additive manufacturing processing.
11. An additive layer obtainable by the additive manufacturing process according to any one or more of claims 1 to 10, wherein the additive layer may comprise one or more layers.
12. The additive layer of claim 11 wherein when the additive layer comprises three layers, the three layers can be a tie layer, a reinforcement layer, and a skin layer;
the bonding layer: the iron-based powder comprises 0.4-0.8 wt% of C, 4.0-6.0 wt% of Cr, 1.3-1.7 wt% of B, 2.5-3.5 wt% of Si, 28-32 wt% of Ni and the balance of Cu;
the addition of C and Si can improve the strength of the metallurgical bonding layer and the wear resistance of the additive manufacturing layer, and also has the function of a transition layer between the bonding layers, so that the generation or the tendency of cracks in additive manufacturing is reduced.
The strengthening material in the strengthening layer comprises the following components in percentage by weight of less than or equal to 0.1 percent of C, cr:17-19%, B:1.5-2.5%, si:1.5-2.5%, ni:8-10%, mo:1-1.5%, V:0.5-1.5% and the balance of Cu.
The name of the surface layer powder is CuCrZr and the proportion is as follows: 0.75 percent of Cr, 0.077 percent of Zr, and the balance of Cu, the specification is 15-53um, and the particle size is as follows: d10:20.5um, D50.
13. The additive layer of claim 12 wherein the additive layer has a thickness of 0.1 to 5.0mm or a thickness of 2mm or more.
14. An additive product, wherein the surface of the additive product is attached with the additive layer as defined in any one of claims 11 to 13, or the additive product is obtained by the additive manufacturing process as defined in any one of claims 1 to 10 and the surface of the additive layer is attached with the additive layer as defined in any one of claims 11 to 13, wherein the product to be additive is an automobile thermoforming mold of Cr12 material, and the automobile thermoforming mold surface of the additive Cr12 material is provided with the additive layer for improving the heat resistance, wear resistance and impact resistance of the mold.
15. A composite laser, wherein the laser beam output by the composite laser can be used in any additive manufacturing process of claims 1-10, can also be used in the process of obtaining any additive layer of claims 11-13, can also be used in any additive manufacturing process of claims 1-10 to obtain any additive layer of claims 11-13, and can also be used in any additive manufacturing process of claims 1-10 to obtain the additive product of claim 14.
16. The composite laser of claim 15, wherein the composite laser is comprised of a single-pass coaxial powder feeder, a shielding gas device, a CCD vision inspection system, a protective mirror system, a water cooling system, a semiconductor QBH connector, and a blue QBH connector.
One or more laser beams pass through a QBH joint and then pass through a multi-wavelength fitting system and then pass through a protective glass system to reach the surface of additive manufacturing, a single-path coaxial powder feeding head is connected to a powder feeder to feed powder, a shielding gas device is connected to nitrogen, the trace is confirmed through a CCD detection system, after the powder passes through the single-path coaxial powder feeding head, the powder falls on the surface to be additivated, and then the multi-wavelength laser beams irradiate the surface of the powder, so that the metallurgical bonding layer is quickly formed on the surface of the powder additive to achieve the additive effect.
17. The additive manufacturing equipment is characterized by comprising a marble platform, a marble portal frame, a component, a multi-wavelength composite additive manufacturing head, a multi-wavelength composite additive manufacturing shielding gas device, a coaxial powder feeding head, a special clamp, a moving platform and a CCD (charge coupled device) vision detection system.
18. The additive manufacturing apparatus of claim 17 wherein the marble gantry is provided with the composite laser of claim 16;
the special fixture comprises servo motor motion platform system, anchor clamps mounting panel, front positioning system, left side positioning system, right side positioning system, front side positioning baffle, motion guide rail system, preceding dust cover protection system and back dust cover protection system, special fixture is used for fixing a position the product that needs the vibration material disk.
CN202110432889.0A 2021-04-21 2021-04-21 Additive manufacturing process, additive layer, additive product and composite laser Pending CN115213408A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110432889.0A CN115213408A (en) 2021-04-21 2021-04-21 Additive manufacturing process, additive layer, additive product and composite laser

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110432889.0A CN115213408A (en) 2021-04-21 2021-04-21 Additive manufacturing process, additive layer, additive product and composite laser

Publications (1)

Publication Number Publication Date
CN115213408A true CN115213408A (en) 2022-10-21

Family

ID=83606343

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110432889.0A Pending CN115213408A (en) 2021-04-21 2021-04-21 Additive manufacturing process, additive layer, additive product and composite laser

Country Status (1)

Country Link
CN (1) CN115213408A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050058163A1 (en) * 2003-09-12 2005-03-17 Lightwave Electronics Corporation High repetition rate passively Q-switched laser for blue laser based on interactions in fiber
WO2019089983A1 (en) * 2017-11-01 2019-05-09 Nuburu, Inc. Multi kw class blue laser system
US20190273365A1 (en) * 2014-08-27 2019-09-05 Nuburu, Inc. Multi kW Class Blue Laser System
CN110273155A (en) * 2019-07-31 2019-09-24 天津玛斯特车身装备技术有限公司 A kind of laser cladding reconstructing technique
CN111347158A (en) * 2020-03-20 2020-06-30 华中科技大学 Compound welding set of semiconductor blue light laser and fiber laser
CN111761205A (en) * 2020-07-10 2020-10-13 上海嘉强自动化技术有限公司 Dual-waveband laser swing welding optical system
CN112108760A (en) * 2020-09-08 2020-12-22 深圳市汉威激光设备有限公司 Annular light spot AMB and blue light composite emitting head of continuous laser

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050058163A1 (en) * 2003-09-12 2005-03-17 Lightwave Electronics Corporation High repetition rate passively Q-switched laser for blue laser based on interactions in fiber
US20190273365A1 (en) * 2014-08-27 2019-09-05 Nuburu, Inc. Multi kW Class Blue Laser System
WO2019089983A1 (en) * 2017-11-01 2019-05-09 Nuburu, Inc. Multi kw class blue laser system
CN110273155A (en) * 2019-07-31 2019-09-24 天津玛斯特车身装备技术有限公司 A kind of laser cladding reconstructing technique
CN111347158A (en) * 2020-03-20 2020-06-30 华中科技大学 Compound welding set of semiconductor blue light laser and fiber laser
CN111761205A (en) * 2020-07-10 2020-10-13 上海嘉强自动化技术有限公司 Dual-waveband laser swing welding optical system
CN112108760A (en) * 2020-09-08 2020-12-22 深圳市汉威激光设备有限公司 Annular light spot AMB and blue light composite emitting head of continuous laser

Similar Documents

Publication Publication Date Title
CN110273155A (en) A kind of laser cladding reconstructing technique
US7009137B2 (en) Laser powder fusion repair of Z-notches with nickel based superalloy powder
CN101397663A (en) Novel repair and reconstruction technique for defect treatment of strip coiler hollow axle
CN104141129A (en) Repairing method for threaded rod
CN107723701A (en) Unimach rises and falls the electromagnetic agitation laser melting coating restorative procedure of frame member crackle
CN110747458A (en) Method for repairing crankshaft of hot-rolling fixed-width press
CN112663051B (en) Laser cladding repair method for local damage of external thread of undercarriage axle
CN114260465B (en) Laser repairing method for thin-wall single crystal turbine blade
CN111545918B (en) Laser polishing and laser shock strengthening manufacturing method for welding or additive repairing area
CN106757011A (en) A kind of laser melting coating reproducing method of worm screw
CN110983103A (en) 3D printing laser repair method for TB6 titanium alloy
CN112139667A (en) Ultrasonic-assisted swing laser welding method for hot stamping formed steel
WO2022222590A1 (en) Additive manufacturing process, additive layer, additive product, and composite laser
CN103614731A (en) Composite roller repairing method using laser rapid prototyping
CN110747462A (en) High-speed laser cladding process
CN115213408A (en) Additive manufacturing process, additive layer, additive product and composite laser
CN114515837B (en) Laser selective melting repair method for blade tip of single crystal turbine blade
CN112210774A (en) Laser cladding repair method for machine tool failure gear
Wang et al. Component repair using laser direct metal deposition
CN115044900A (en) Remanufacturing process for diesel engine camshaft of mining heavy-duty vehicle
CN115261870A (en) Short-process composite ultra-high-speed laser cladding processing method based on Haokeng technology
CN103498151A (en) Laser cladding method for surface of worm
CN111945155A (en) Method for double-cylinder synchronous powder feeding, melting and depositing composite cladding layer based on 30CrMnSiA steel
CN111893485A (en) Method for double-cylinder synchronous powder feeding, melting and depositing composite cladding layer based on 35# steel
Karşi et al. Optimization of Laser Cladding Process Parameters of a Martensitic Stainless Steel Coating on GGG70L Ductile Cast Iron.

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