EP3536827A1 - Procédé de traitement de surface destiné à une tête de repoussage de tantale - Google Patents

Procédé de traitement de surface destiné à une tête de repoussage de tantale Download PDF

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Publication number
EP3536827A1
EP3536827A1 EP18761041.5A EP18761041A EP3536827A1 EP 3536827 A1 EP3536827 A1 EP 3536827A1 EP 18761041 A EP18761041 A EP 18761041A EP 3536827 A1 EP3536827 A1 EP 3536827A1
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EP
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Prior art keywords
spinneret
tantalum
lithium
film
mixed melt
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EP18761041.5A
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German (de)
English (en)
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EP3536827B9 (fr
EP3536827A4 (fr
EP3536827B1 (fr
Inventor
Yuzhong Liu
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Beijing Huayu Chuangxin Science & Trade Co Ltd
Beijing Huayu Chuangxin Ta-Nb Science & Technology Co Ltd
Original Assignee
Beijing Huayu Chuangxin Science & Trade Co Ltd
Beijing Huayu Chuangxin Ta-Nb Science & Technology Co Ltd
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Priority claimed from PCT/CN2018/077938 external-priority patent/WO2018157867A1/fr
Publication of EP3536827A1 publication Critical patent/EP3536827A1/fr
Publication of EP3536827A4 publication Critical patent/EP3536827A4/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D01D4/022—Processes or materials for the preparation of spinnerettes

Definitions

  • the present invention relates to a surface treatment method of tantalum spinneret. More specifically, the present invention relates to a surface treatment method of tantalum spinneret for wet spinning or dry-wet spinning, and more particularly to a surface treatment method of tantalum spinneret.
  • the process for producing chemical fiber is different, and the requirements for the spinneret (plate) are also different.
  • chemical fiber production usually employs three processes, namely, melt spinning, dry spinning (also called dry-wet spinning), and wet spinning.
  • melt spinning the spinneret used needs to withstand a pressure of up to several hundred atmospheric pressures. Therefore, the material for manufacturing the spinneret is required to have good physical and mechanical properties, and the thickness of the spinneret reaches 10 mm to 30 mm.
  • wet spinning the spinneret used is subjected to much less pressure and its thickness is generally between 0.2 and 0.75 mm.
  • the pressure that the spinneret needs to withstand and the thickness required for the spinneret are between those for the spinneret used for melt spinning and the spinneret used for the wet spinning. Since wet spinning is carried out in a strong acid and alkali environment, the spinneret used needs to have strong corrosion resistance. Therefore, in the early stage of chemical fiber production, in most wet spinning processes, for example, in the production process of viscose fiber, acrylic yarn, etc., the spinneret is made of a noble metal such as an alloy of gold, platinum, rhodium or palladium.
  • the surface-treated tantalum spinneret can reduce the adsorption of charged waste around the micropores of the spinneret, or affect the deposition speed, and thus affect the plugging of the spinneret, thereby improving the spinnability index (such as broken filament, spinneret change rate, etc.).
  • the surface treatment also has an effect on the surface roughness, and if the roughness is lowered, the spinnability is better.
  • the processed tantalum spinneret has been tried to reduce the roughness of the micropore wall by the surface treatment process, thereby improving the spinnability of the spinneret, but there has been no effective method.
  • the surface treatment after the spinneret processing needs to balance the surface properties, surface finish and surface hardness to obtain a suitable comprehensive and optimal effect, but the most critical aspects related to the spinnability of the spinneret are the surface properties and finish to meet the different requirements of different chemical fiber varieties.
  • a nitriding only tantalum spinneret can be used for wet spinning of acrylic fibers, but for wet spinning of viscose fibers, the spinnability is poor.
  • Patents ZL 85101505 , ZL 86102269 (hereinafter referred to as the first generation patent) and patent ZL 02106915.8 granted in 2006 (hereinafter referred to as the second generation patent) are widely used in the chemical fiber wet spinning in which spinnerets are prepared by replacing gold with tantalum.
  • the produced tantalum spinneret coated with lithium-containing compound is similar to the noble metal gold-platinum (rhodium) alloy spinneret, and even superior to the noble metal gold-platinum (rhodium) alloy spinneret.
  • the spinnability of the gold-platinum spinneret and the coated tantalum spinneret decreased, but the coated tantalum spinneret decreased more.
  • spinning special fibers such as spinning matt fibers
  • it is necessary to add a certain amount of titanium dioxide powder particles to the raw solution when spinning flame retardant fibers, it is necessary to add a certain amount of particulate flame retardant to the raw solution.
  • the spinnability of the coated tantalum spinneret is significantly inferior to that of the gold-platinum spinneret.
  • the spinneret change period of the above-mentioned coated tantalum spinneret is only 8 hours, otherwise the quality of the filament will be affected, but the gold-platinum spinneret can be spun for 16 to 24 hours. This is because the roughness of the micropore wall of the coated tantalum spinneret is larger than that of the gold-platinum spinneret. If the powdery additive is added during the spinning of the above special fiber, or if the particles appear in the raw solution since the spinning process is unstable, it is desirable that the roughness of the micropore wall of the spinneret is lower, otherwise the pores are more likely to be blocked, thereby affecting the spinnability of the spinneret.
  • the present invention relates to a surface treatment method of tantalum spinneret, in particular to a surface treatment method of tantalum spinneret for wet spinning, wherein the method comprises the following steps:
  • the method of the present invention further comprises a polishing step (d): subjecting the fiber outlet face of the tantalum spinneret treated in step (c) to a polishing treatment to remove the film layer containing lithium-containing compound on the surface of the fiber outlet face.
  • step (a) the Ta 2 O 5 film formed on the tantalum spinneret is an amorphous Ta 2 O 5 film.
  • a layer of amorphous Ta 2 O 5 film is formed on the tantalum spinneret by anodization in step (a).
  • the tantalum spinneret is placed in an oxygen-containing electrolyte solution at room temperature to 380°C, preferably room temperature to 300°C, and an anode voltage of 3 to 800V is applied constantly for 0.01 to 2 hours, with a voltage-increasing current density of 1 to 200 mA/cm 2 to form a layer of amorphous Ta 2 O 5 film.
  • step (a) if the solution temperature is high, the applied voltage should be low, and vice versa. For example, for a 0.01% H 3 PO 4 solution at room temperature, a voltage of up to 600V can be applied. Regardless of the solution, the applied voltage should be below the flashover voltage of the solution.
  • the oxygen-containing electrolyte solution may be an aqueous solution, a non-aqueous solution, or a mixture of an aqueous electrolyte and an organic compound.
  • the aqueous oxygen-containing electrolyte may be, for example, an aqueous solution of an acid, a base, or a salt.
  • the solution temperature is from room temperature (about 25°C) to 95°C
  • the anode voltage is 5 to 600V
  • the constant voltage time is within 60 to 90 minutes.
  • the temperature is too high, the water volatilizes too quickly.
  • the anode voltage should be low.
  • a high solution temperature, a high anode voltage, and a long constant voltage time tend to result in crystallization of the amorphous anodic oxide film, which should be prevented because the roughness is increased after crystallization or partial crystallization of the amorphous Ta 2 O 5 film.
  • the non-aqueous oxygen-containing electrolyte may be anhydrous concentrated sulfuric acid or a molten salt or a mixture of a molten salt and a base, such as potassium nitrate, sodium nitrate, lithium nitrate, or a mixture thereof with a base such as lithium, sodium or potassium-containing base.
  • the melting temperature should be controlled to the melting point of the molten salt to below 380°C, because tantalum will be significantly oxidized above 400°C. A voltage of 3 to 66V is applied.
  • oxygen-containing electrolyte solution may be a mixture of an aqueous electrolyte and an organic compound such as ethanol, ethylene glycol, n-butanol or the like.
  • the temperature of the aqueous solution should be below 95°C, otherwise the water volatilizes quickly, and it is difficult to control.
  • step (c) When the coating temperature in step (c) is from 250°C to 430°C, preferably from 300°C to 400°C, more preferably from 300°C to 350°C, step (a) of forming a layer of Ta 2 O 5 film before coating on the tantalum spinneret may be omitted.
  • the spinneret in step (c), is placed in an oxygen-containing inorganic lithium salt (such as LiNO 3 ) or a mixed melt of oxygen-containing inorganic lithium salt and lithium hydroxide, or a mixed melt liquid of a salt and lithium hydroxide or a mixed melt liquid of a lithium salt and an oxygen-containing salt at a temperature of 250°C to 650°C, preferably 250°C to 430°C, and an anode voltage of 1 to 66V is applied constantly for 0.01 to 200 hours, with a voltage-increasing current density of 1 to 1000 mA/cm 2 to form a film layer of lithium-containing compound.
  • an oxygen-containing inorganic lithium salt such as LiNO 3
  • a mixed melt liquid of a salt and lithium hydroxide or a mixed melt liquid of a lithium salt and an oxygen-containing salt at a temperature of 250°C to 650°C, preferably 250°C to 430°C
  • an anode voltage of 1 to 66V is applied constantly for
  • the mixed melt or the mixed melt liquid has a temperature of 300°C to 520°C, the applied anode voltage is 5 to 25V, and the voltage-increasing current density is 5 to 20 mA/cm 2 .
  • an ultrasonic generator can be placed in the mixed melt or the mixed melt liquid in step (c).
  • the molten salt electrochemical method in step (c) is a molten lithium salt electrochemical method.
  • the surface treatment method of the present invention comprises subjecting the tantalum spinneret to a nitriding treatment prior to step (a), as in accordance with the method of step (b) of the specification of ZL02106915.8 .
  • the nitriding treatment may not be performed prior to step (a). Whether or not nitriding treatment is carried out is determined according to different fiber spinning requirements.
  • a fiber type having a low spinning speed and a low-pressure requirement may not be nitrided in advance, which can save costs.
  • a relatively low temperature such as 400°C or lower is employed, a nitriding treatment may be employed in order to obtain a high hardness,
  • the tantalum spinneret suitable for use in the present invention comprises a pure tantalum spinneret and a tantalum alloy spinneret, wherein the tantalum alloy spinneret is preferably a tantalum-niobium alloy spinneret.
  • Table 1 shows that the film roughness of the coated tantalum spinneret of the present invention is nearly four times lower than those of the coated tantalum spinnerets of the prior art patents ZL 85101505 and ZL86102269 , and 1 to 2 times lower than that of the coated tantalum spinneret of the patent ZL02106915.8 .
  • the film layer of the micropore wall of the spinneret has the same roughness as the film layer on the surface of the spinneret, or has a corresponding relationship.
  • the roughness of the film layer of lithium-containing compound formed after subjecting the amorphous Ta 2 O 5 film which is obtained by using different anodization voltages in step (a) of the present invention to the treatment of step (c) is shown in Table 2.
  • Table 2. Effect of different anodization voltages in step (a) on the roughness of film layer of lithium-containing compound Anodizing voltage 130V 240V 420V 30V (molten salt) Roughness 0.027 0.051 0.061 0.053 Note: 1.
  • the voltage of the oxidation is increased, and the roughness of the film layer of lithium-containing compound after the coating is increased, so that the voltage of the anodization is not too high.
  • Anodizing forms an amorphous Ta 2 O 5 film.
  • the voltage for anodization in step (a) is preferably between 5 and 240V, wherein the treatment of the molten salt is to apply an anode voltage of 30V constantly for 1.5 hours at 300°C. If a higher anodization voltage such as 480V is used, the constant voltage time is shorter.
  • the roughness of the obtained film layer of lithium-containing compound is affected by the solution temperature, the applied anode voltage, and the constant voltage time of step (c). That is, as the temperature rises, the anode voltage increases, and the time extension increases the roughness of the film layer of lithium-containing compound.
  • Table 3 the change with voltage is shown in Table 3: Table 3. Changes of roughness of the film layer of lithium-containing compound in step (c) with anode voltage Anode voltage 10V 25V 30V Film layer roughness 0.027 0.096 0.127 Hardness (HV) 346.8 406.7 433.3 Note: 1.
  • step (a) The anodization of step (a) was carried out in an aqueous solution of phosphoric acid ethylene glycol, and a voltage of 60V was applied thereto constantly for 1.0 hour. 2.
  • the solution used in step (c) was pure LiNO 3 at 488°C and a constant voltage for 1.5 hours.
  • step (b) of the present invention the amorphous Ta 2 O 5 film on the fiber outlet face of the spinneret is removed and the amorphous Ta 2 O 5 film on the micropore inner wall of the spinneret is retained, that is because if there is an amorphous Ta 2 O 5 film on the fiber outlet face of the spinneret and then step (c) electrochemical coating is performed, the hardness of the surface of the obtained coating is much lower than that of the surface of the coating obtained by electrochemical coating after removing the amorphous Ta 2 O 5 film by polishing, as shown in Table 4.
  • step (b) is not employed before step (c), i.e., step (c) is directly performed without removing the amorphous Ta 2 O 5 film, and the surface hardness of the obtained spinneret is adjusted to be close to the surface hardness of the noble metal spinneret, for example, both around HV220, which can also be adapted to some specific spinning conditions, such as chemical fiber with low spinning speed and low spinning pressure, to simplify the operation process and reduce the cost.
  • Table 4 4.
  • step (c) In the case when the coating temperature in step (c) was lowered to 350°C, an anode voltage of 10V or 39V is applied, and the reaction time is 20 hours, 30 hours, or 40 hours, the roughness of the film layer of lithium-containing compound is lower, and the spinnability is better.
  • the measured roughness and hardness are shown in Table 5.
  • 1 indicates a fiber outlet face of a tantalum spinneret
  • 2 indicates a spinneret body
  • 3 indicates a Ta 2 O 5 film
  • 6 indicates a film layer of lithium-containing compound
  • 7 indicates a modified layer
  • the modified layer is the film layer of lithium-containing compound plus a transition layer
  • 8 indicates a transition layer.
  • Example 1 the surface treatment method for wet spinning of the present invention is illustrated.
  • the steps of Example 1 are as follows:
  • Table 7 shows the results of a combined spinneret formed by a combination of 45 of single spinnerets of ⁇ 16*2600 holes*0.05.
  • the conditions for forming the three coated tantalum spinnerets listed in Table 7 are shown in the notes of Table 1.
  • Example 2 the surface treatment method of spinneret for wet spinning of the present invention is illustrated.
  • the steps of Example 2 are as follows:
  • the above-mentioned 27 anodized and coated tantalum spinneret were mounted on a base plate of a viscose short-staple stainless-steel combined spinneret, and were subjected to a viscose short-staple flame-retardant fiber spinning test in comparison with a coated tantalum spinneret which was not anodized before coating of the prior art.
  • the results showed that the spinneret change period of the coated tantalum spinneret of the present invention was 16 hours, and the best second-generation coated tantalum spinneret (i.e., patent ZL2101015.8 ) in the prior art had a spinneret change period of 8 hours, therefore, the time had been doubled.
  • the method is also applicable to the tantalum-niobium spinneret made of tantalum-niobium alloy which is cheaper, but the corrosion resistance and processing performance of tantalum-niobium are inferior to those of pure tantalum.
  • the tantalum-niobium alloy spinneret is superior to the pure niobium spinneret, thus can be considered for some wet spinning without strong acid and alkali requirements.
  • Example 3 the surface treatment method for wet spinning of the present invention is illustrated.
  • the steps of Example 3 are as follows:
  • Example 4 the surface treatment method for wet spinning of the present invention is illustrated.
  • the steps of Example 4 are as follows:
  • Example 5 the surface treatment method for wet spinning of the present invention is illustrated.
  • the steps of Example 5 are as follows:
  • Example 6 the surface treatment method for wet spinning of the present invention is illustrated.
  • the steps of Example 6 are as follows:
  • the four coated tantalum spinnerets prepared in Examples 3 to 6 were subjected to aramid III spinning test in comparison with the coated tantalum spinneret manufactured by the prior art patent ZL02106915.8 .
  • the spinning cycle of the coated tantalum spinneret of the prior patent ZL02106915.8 was about 5-7 days on average, and the spinning cycle of the coated tantalum spinneret of the present invention was more than 20 days on average.
  • the experimental results are shown in Table 9, and thus an unexpected technical effect was obtained. Table 9.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Textile Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP18761041.5A 2017-03-03 2018-03-02 Procédé de traitement de surface destiné à une tête de repoussage de tantale Active EP3536827B9 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201710124797 2017-03-03
CN201710587999.8A CN108531906B (zh) 2017-03-03 2017-07-19 钽喷丝头的表面处理方法
PCT/CN2018/077938 WO2018157867A1 (fr) 2017-03-03 2018-03-02 Procédé de traitement de surface destiné à une tête de repoussage de tantale

Publications (4)

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EP3536827A1 true EP3536827A1 (fr) 2019-09-11
EP3536827A4 EP3536827A4 (fr) 2020-04-29
EP3536827B1 EP3536827B1 (fr) 2022-01-26
EP3536827B9 EP3536827B9 (fr) 2022-05-18

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EP (1) EP3536827B9 (fr)
JP (1) JP6808848B2 (fr)
CN (1) CN108531906B (fr)
ES (1) ES2908746T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111005050A (zh) * 2020-02-19 2020-04-14 南昌航空大学 一种提高烧结钕铁硼磁体耐蚀性双涂层的制备方法
CN113913953A (zh) * 2019-11-19 2022-01-11 中国石油化工股份有限公司 一种扁平形腈纶纤维的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678546A (en) * 1985-03-27 1987-07-07 North China Research Institute Of Electro-Optics Process for providing lithium tantalum oxide coated tantalum articles with improved wear resistance
CN85101505B (zh) * 1985-04-01 1988-03-30 华北光电技术研究所 钽铌器件熔盐电解法制膜及产品
JPH0660436B2 (ja) * 1986-03-28 1994-08-10 ユ ツオン リユ タンタル、ニオブまたはその合金製物品の保護膜およびその製法
CN86102269B (zh) * 1986-04-09 1988-11-23 华北光电技术研究所 带膜钽铌喷丝头(板)的制造方法及应用
CN2151155Y (zh) * 1992-11-15 1993-12-29 李士华 钽材制品离子电解镀膜
CN1279224C (zh) * 2001-04-09 2006-10-11 北京华宇创新科贸有限责任公司 用于湿法纺丝的钽喷丝头的表面处理方法
CN1428465A (zh) * 2001-12-27 2003-07-09 北京华宇创新科贸有限责任公司 用于湿法纺丝的钽喷丝头的表面处理方法
CN100443629C (zh) * 2006-06-22 2008-12-17 上海交通大学 钽喷丝头表面化学气相沉积金刚石薄膜强化方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113913953A (zh) * 2019-11-19 2022-01-11 中国石油化工股份有限公司 一种扁平形腈纶纤维的制备方法
CN113913953B (zh) * 2019-11-19 2022-07-01 中国石油化工股份有限公司 一种扁平形腈纶纤维的制备方法
CN111005050A (zh) * 2020-02-19 2020-04-14 南昌航空大学 一种提高烧结钕铁硼磁体耐蚀性双涂层的制备方法

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EP3536827B9 (fr) 2022-05-18
ES2908746T9 (es) 2022-06-13
CN108531906B (zh) 2020-05-29
EP3536827A4 (fr) 2020-04-29
ES2908746T3 (es) 2022-05-03
EP3536827B1 (fr) 2022-01-26
JP2020509250A (ja) 2020-03-26
JP6808848B2 (ja) 2021-01-06
CN108531906A (zh) 2018-09-14

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