CN115975612B - Subway shield foaming agent and preparation method thereof - Google Patents
Subway shield foaming agent and preparation method thereof Download PDFInfo
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- CN115975612B CN115975612B CN202210683545.1A CN202210683545A CN115975612B CN 115975612 B CN115975612 B CN 115975612B CN 202210683545 A CN202210683545 A CN 202210683545A CN 115975612 B CN115975612 B CN 115975612B
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- 239000004088 foaming agent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002994 raw material Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005187 foaming Methods 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 14
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000004711 α-olefin Substances 0.000 claims abstract description 13
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims abstract description 11
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 11
- 239000005639 Lauric acid Substances 0.000 claims abstract description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- NGOZDSMNMIRDFP-UHFFFAOYSA-N 2-[methyl(tetradecanoyl)amino]acetic acid Chemical compound CCCCCCCCCCCCCC(=O)N(C)CC(O)=O NGOZDSMNMIRDFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 28
- 229940060304 sodium myristoyl sarcosinate Drugs 0.000 claims description 9
- KHCOJQDJOCNUGV-UHFFFAOYSA-M sodium;2-[methyl(tetradecanoyl)amino]acetate Chemical compound [Na+].CCCCCCCCCCCCCC(=O)N(C)CC([O-])=O KHCOJQDJOCNUGV-UHFFFAOYSA-M 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 7
- -1 lauric acid imidazoline quaternary ammonium salt Chemical class 0.000 claims description 6
- 239000002689 soil Substances 0.000 abstract description 7
- 230000005641 tunneling Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 description 11
- 239000006260 foam Substances 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Abstract
The invention discloses a subway shield foaming agent which is prepared from the following raw materials in percentage by mass: 5-10% of alpha-olefin sulfonate surfactant, 5-10% of cocamidopropyl betaine, 2-6% of cetyl trimethyl ammonium chloride, 1-5% of myristoyl sarcosine sodium, 1-5% of lauric acid imidazoline quaternary ammonium amphoteric surfactant, 0.5-1% of polyacrylamide and the balance of water. The subway shield foaming agent prepared by the method has the viscosity of 0.6-1.4 Pa.s at 25 ℃, the half-life period of 35-45 min and the foaming multiplying power of 24-28 times, and has excellent foaming capacity and foaming stability; the soil body flowability and water stopping performance can be effectively improved, the cutter head has good lubricity, the torque of the cutter head can be obviously reduced, the tunneling speed is greatly improved, and the service life of the cutter head is prolonged.
Description
Technical Field
The invention relates to the field of shield construction, in particular to a subway shield foaming agent and a preparation method thereof.
Background
With the development of scientific technology in China, more and more cities are planning and constructing subways, and the earth pressure balance shield construction method is a main flow mode of current construction. The earth pressure balance shield construction method is not influenced by the aspects of topography, engineering quality, construction progress, safety, environment and the like, so that the shield construction method has obvious technical and economic superiority especially under the conditions of poor stratum condition, complex geological condition, high groundwater level and the like. However, aiming at the characteristics of complex terrains and landforms, a series of difficulties such as mud spraying, sand surging, cake forming, blocking and the like exist, the prior art generally utilizes a foaming agent to improve soil, so that the shield machine is constructed in different geological layers, the abrasion and blocking of a cutter can be reduced, the tunneling speed is improved, and the cost is saved. The foaming agent is generally dispersed in water by compounding a surfactant and adding a certain foam stabilizer, tackifier and the like.
Patent CN 108070383A discloses a foam stabilizing and lasting soil pressure balance shield foaming agent which is prepared from the following raw materials in percentage by weight: 12% -15% of sodium dodecyl sulfate; 3 to 6 percent of fatty alcohol polyoxyethylene ether sodium sulfate; 0.1 to 0.3 percent of dodecanol; 2% -4% of hexene glycol; 3% -5% of cocoamidopropyl betaine; NH (NH) 3 ·H 2 O1-1.8%; the balance being water. Patent CN106753408A discloses a novel shield foaming agent comprising: the adhesive comprises at least the following components in parts by weight: 5-10 parts of sodium dodecyl sulfate; 1-10 parts of sodium dodecyl polyoxyethylene ether sulfate; 0.1 to 10 parts of laurinol polyoxyethylene ether; 0.1 to 10 portions of isomeric tridecanol polyoxyethylene ether; 0.1 to 10 parts of sodium chloride; 80-100 parts of water. The novel shield foaming agent provided by the invention has excellent foaming performance and stability. Patent CN104946263a discloses a soil pressure balance shield foaming agent, which is prepared from the following raw materials in percentage by weight: 4-15% of sodium dodecyl sulfate, 1-10% of cetyl trimethyl ammonium chloride, 2-8% of cocamidopropyl betaine, 1-5% of dodecyl dimethyl ammonium oxide, 0.1-0.5% of disodium ethylenediamine tetraacetate, 0.1-2.0% of tackifier and the balance of water.
The shield construction in China is also widely applied in recent years, and most of the shield construction adopts imported materials, so that the cost is high.
Disclosure of Invention
Based on the defects and requirements of the prior art, the invention aims to provide the subway shield foaming agent and the preparation method thereof, and the foaming agent provided by the invention has the characteristics of stability, long foam half-life and high permeability, can obviously reduce the torque of a cutter head, and can well meet the requirement of improving the dregs in the tunneling process of the earth pressure balance shield machine.
In order to solve the technical problems, the invention adopts the following technical scheme:
the subway shield foaming agent is prepared from the following raw materials in percentage by mass:
further, the subway shield foaming agent is prepared from the following raw materials in percentage by mass:
further, the subway shield foaming agent is prepared from the following raw materials in percentage by mass:
further, the pH of the subway shield foaming agent is 7.5-8.0, and the density at 25 ℃ is 1.02-1.05 g.cm -3 The viscosity is 0.6 to 1.4 Pa.s at 25 ℃, the half life is 35 to 45min, and the foaming multiplying power is 24 to 28 times.
A preparation method of a subway shield foaming agent comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw materials;
(2) And (3) placing water into a container, sequentially adding the alpha-olefin sulfonate surfactant, the cocamidopropyl betaine, the cetyltrimethylammonium chloride, the sodium myristoyl sarcosinate, the lauroyl imidazoline quaternary ammonium amphoteric surfactant and the polyacrylamide into the water under the condition of stirring, and uniformly stirring.
Further, the stirring speed is 20-30 r/min, and the stirring time is 10-20 min.
The invention adopts alpha-olefin sulfonate surfactant, cocamidopropyl betaine and cetyltrimethylammonium chloride as main foaming components through the compounding of the surfactant, so as to ensure the basic foaming performance; the amino acid type surface active sodium myristoyl sarcosinate is matched with the water-soluble sodium myristoyl sarcosinate, so that the produced foam is rich and fine; the lauric acid imidazoline quaternary ammonium salt amphoteric surfactant has smaller surface tension, can reduce the tendency of the surface tension of the foaming agent to be far greater than the tendency of polymerization to form micelle, has the critical micelle concentration which is several orders of magnitude lower than that of the common surfactant, and further controls the surface tension of the foaming agent to be 20-30 mN.m -1 To exert the optimal foaming ability and stability.
Compared with the prior art, the invention has the following beneficial effects:
(1) The subway shield foaming agent prepared by the method has the viscosity of 0.6-1.4 Pa.s at 25 ℃, the half-life period of 35-45 min and the foaming multiplying power of 24-28 times, and has excellent foaming capacity and foaming stability.
(2) The soil body flowability and water stopping performance can be effectively improved, the cutter head has good lubricity, the torque of the cutter head can be obviously reduced, the tunneling speed is greatly improved, and the service life of the cutter head is prolonged.
(3) The foam produced by the foaming agent has high permeability, can quickly permeate into soil, effectively prevents blocking phenomenon, and enables tunneling to be carried out smoothly.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
the preparation method of the subway shield foaming agent comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw materials;
(2) And (3) placing water into a container, sequentially adding the alpha-olefin sulfonate surfactant, the cocamidopropyl betaine, the cetyltrimethylammonium chloride, the sodium myristoyl sarcosinate, the lauroyl imidazoline quaternary ammonium amphoteric surfactant and the polyacrylamide into the water under the condition of stirring, and uniformly stirring. Wherein the stirring speed is 20r/min and the stirring time is 10min.
Example 2
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
the preparation method of the subway shield foaming agent comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw materials;
(2) And (3) placing water into a container, sequentially adding the alpha-olefin sulfonate surfactant, the cocamidopropyl betaine, the cetyltrimethylammonium chloride, the sodium myristoyl sarcosinate, the lauroyl imidazoline quaternary ammonium amphoteric surfactant and the polyacrylamide into the water under the condition of stirring, and uniformly stirring. Wherein, the stirring speed is 30r/min, and the stirring time is 20min.
Example 3
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
the preparation method of the subway shield foaming agent comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw materials;
(2) And (3) placing water into a container, sequentially adding the alpha-olefin sulfonate surfactant, the cocamidopropyl betaine, the cetyltrimethylammonium chloride, the sodium myristoyl sarcosinate, the lauroyl imidazoline quaternary ammonium amphoteric surfactant and the polyacrylamide into the water under the condition of stirring, and uniformly stirring. Wherein, the stirring speed is 25r/min, and the stirring time is 15min.
Example 4
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
the preparation method of the subway shield foaming agent comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw materials;
(2) And (3) placing water into a container, sequentially adding the alpha-olefin sulfonate surfactant, the cocamidopropyl betaine, the cetyltrimethylammonium chloride, the sodium myristoyl sarcosinate, the lauroyl imidazoline quaternary ammonium amphoteric surfactant and the polyacrylamide into the water under the condition of stirring, and uniformly stirring. Wherein, the stirring speed is 20r/min, and the stirring time is 20min.
Example 5
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
the preparation method of the subway shield foaming agent comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw materials;
(2) And (3) placing water into a container, sequentially adding the alpha-olefin sulfonate surfactant, the cocamidopropyl betaine, the cetyltrimethylammonium chloride, the sodium myristoyl sarcosinate, the lauroyl imidazoline quaternary ammonium amphoteric surfactant and the polyacrylamide into the water under the condition of stirring, and uniformly stirring. Wherein the stirring speed is 20r/min and the stirring time is 10min.
1. In order to better embody the functions of the raw materials of the foaming agent, the subway shield foaming agent prepared in the invention examples 1-5 is compared with the model of the imported foaming agent Basoff SLF 33. The results of the basic performance tests are reported in table 1.
TABLE 1
Compared with the Basv MEYCO SLF 33 model, the subway shield foaming agent prepared by the invention has more excellent foaming multiplying power and stability, and can reach an import level. Can be used as a replacement product of imported foaming agent in the construction process, and can effectively reduce the construction cost.
2. We also prepared a control test group with example 5 as a reference, wherein:
comparative example 1
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
comparative example 2
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
comparative example 3
The subway shield foaming agent is prepared from the following raw materials in percentage by mass:
the results of the basic performance tests are reported in table 2.
TABLE 2
As can be seen from the data in table 2, the foam agent comprising only the α -olefin sulfonate surfactant, cocamidopropyl betaine, and cetyl trimethyl ammonium chloride also had a certain foaming property, but the properties were also improved in all respects after the addition of sodium myristoyl sarcosine, particularly the foam fineness was significantly changed; this suggests that sodium myristoyl sarcosine is advantageous for foam formation into fine foam within the above-described formulation system. The surface tension of the system is changed from 41.1 mN.m by lauric acid imidazoline quaternary ammonium salt amphoteric surfactant -1 Reduced to 33.6 mN.m -1 The foaming multiplying power and half-life are correspondingly improved, so that the lauric acid imidazoline quaternary ammonium salt amphoteric surfactant can reduce the surface tension of a system, further improve the foaming multiplying power and half-life, and effectively improve the foaming capacity and stability.
In conclusion, the subway shield foaming agent prepared by the invention has excellent performance in the aspects of soil improvement, gushing prevention, blocking prevention and the like, can effectively improve the tunneling speed and reduce the construction cost.
It should be understood that the embodiments described herein are for illustrative purposes only and are not intended to limit the present invention to the particular embodiments disclosed, as various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.
Claims (3)
1. The subway shield foaming agent is characterized by being prepared from the following raw materials in percentage by mass:
alpha-olefin sulfonate surfactant 5-10%
5 to 10 percent of cocoamidopropyl betaine
Cetyl trimethyl ammonium chloride 2-6%
1 to 5 percent of myristoyl sarcosine sodium
1 to 5 percent of lauric acid imidazoline quaternary ammonium salt amphoteric surfactant
0.5 to 1 percent of polyacrylamide
The balance being water;
the pH of the subway shield foaming agent is 7.5-8.0, and the density at 25 ℃ is 1.02-1.05 g.cm -3 The viscosity is 0.6 to 1.4 Pa.s at 25 ℃, the half life is 35 to 45min, and the foaming multiplying power is 24 to 28 times;
the preparation method of the subway shield foaming agent comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw materials;
(2) Placing water into a container, sequentially adding alpha-olefin sulfonate surfactant, cocamidopropyl betaine, cetyltrimethylammonium chloride, sodium myristoyl sarcosinate, lauroyl imidazoline quaternary ammonium amphoteric surfactant and polyacrylamide into the water under the condition of stirring, and uniformly stirring;
the stirring speed is 20-30 r/min, and the stirring time is 10-20 min.
2. The subway shield foaming agent according to claim 1, which is characterized by being prepared from the following raw materials in percentage by mass:
6 to 8 percent of alpha-olefin sulfonate surfactant
6 to 8 percent of cocoamidopropyl betaine
3 to 5 percent of hexadecyl trimethyl ammonium chloride
2 to 4 percent of myristoyl sarcosine sodium
2 to 4 percent of lauric acid imidazoline quaternary ammonium salt amphoteric surfactant
0.6 to 0.8 percent of polyacrylamide
The balance being water.
3. The subway shield foaming agent according to any one of claims 1 to 2, which is characterized by being prepared from the following raw materials in percentage by mass:
alpha-olefin sulfonate surfactant 7.4%
Cocoamidopropyl betaine 6.5%
Cetyl trimethyl ammonium chloride 4.3%
Myristoyl sarcosine sodium 3.2%
2.8 percent of lauric acid imidazoline quaternary ammonium salt amphoteric surfactant
Polyacrylamide 0.65%
The balance being water.
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| CN202210683545.1A CN115975612B (en) | 2022-06-16 | 2022-06-16 | Subway shield foaming agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210683545.1A CN115975612B (en) | 2022-06-16 | 2022-06-16 | Subway shield foaming agent and preparation method thereof |
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| CN115975612B true CN115975612B (en) | 2024-02-09 |
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|---|---|---|---|---|
| CN102430364A (en) * | 2011-09-09 | 2012-05-02 | 中交武汉港湾工程设计研究院有限公司 | Composite stratum waste soil improving foam additive |
| CN103864334A (en) * | 2014-02-12 | 2014-06-18 | 东莞市明洁隧道建设材料有限公司 | Environment-friendly foaming agent for earth pressure balance shield tunneling machine |
| CN104946263A (en) * | 2015-04-02 | 2015-09-30 | 厦门诺恩斯科技有限公司 | Earth pressure balance shield foaming agent |
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| CN108531187A (en) * | 2018-04-11 | 2018-09-14 | 北京市政建设集团有限责任公司 | A kind of balancing earth-pressure shielding machine construction foaming agent and preparation method |
| CN108774535A (en) * | 2018-06-22 | 2018-11-09 | 湖北工程学院 | A kind of special foaming agent of shield machine and its preparation method and application |
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2022
- 2022-06-16 CN CN202210683545.1A patent/CN115975612B/en active Active
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| CN115975612A (en) | 2023-04-18 |
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