CN111807314A - Copper oxide nano whisker material with rapid sterilization and large contact surface - Google Patents
Copper oxide nano whisker material with rapid sterilization and large contact surface Download PDFInfo
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- CN111807314A CN111807314A CN202010577160.8A CN202010577160A CN111807314A CN 111807314 A CN111807314 A CN 111807314A CN 202010577160 A CN202010577160 A CN 202010577160A CN 111807314 A CN111807314 A CN 111807314A
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- copper oxide
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- nano whisker
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 41
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims description 12
- 230000001954 sterilising effect Effects 0.000 title abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 title abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 241000894006 Bacteria Species 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 208000015181 infectious disease Diseases 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- -1 clothing Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/04—Networks or arrays of similar microstructural devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
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- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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Abstract
The invention provides a preparation method of a copper oxide nano whisker structure attached to the surface of metal copper, which comprises the following steps: 1) selecting a cathode electrode; 2) preparing a copper oxide nano whisker structure on a metal copper substrate, and selecting the components and the content of an electrolyte; 3) preparing a copper oxide nano whisker structure on a metal copper substrate, and selecting oxidation time and voltage; 4) preparing the copper oxide nano whisker structure by using the cathode electrode, the electrolyte and the experimental parameters selected in the steps 1), 2) and 3). The preparation method adopted by the invention is simple to operate, low in cost and suitable for large-area preparation; larger specific surface area can be obtained by adjusting experiment parameters; the prepared copper oxide nano whisker structure has stronger sterilization activity on various bacteria, can be used for surfaces needing direct contact in hospitals and various environments, such as handrails, doorknobs and the like, and reduces the spread and infection of the bacteria; the copper oxide nano whisker structure is directly attached to the metal copper, and secondary pollution to the environment can not be caused.
Description
Technical Field
The invention belongs to the field of material science, and relates to a preparation method of a copper oxide nano whisker structure which can realize rapid sterilization and is attached to the surface of metal copper.
Background
Improper or excessive use of antibiotics, as well as the inevitable evolutionary nature of bacteria, can lead to the production of resistant bacterial strains. For example: methicillin-resistant staphylococcus aureus (MRSA) was observed within two years after penicillin was found. Because the drug-resistant strains have the characteristics of wide propagation, rapid evolution and the like, and the effectiveness of the conventional antibacterial method on the drug-resistant strains is gradually reduced, the threat to human beings is increased. Therefore, researchers have begun to research and develop new materials having antibacterial effects. To date, a variety of materials have been developed and produced, including plastics, ceramics, clothing, metals and metal alloys, etc., having different antimicrobial properties. Metals and metal alloys exhibit cheaper and more stable antibacterial properties and are environmentally friendly compared to other chemical polymer based materials. Over the last several centuries, various metals having antibacterial properties have been reported to minimize the spread of infectious diseases by preventing bacterial contamination, and have been commercially used in industrial fields including agriculture, health care, food and pharmaceutical packaging, and the like. Copper and silver are the two most widely used metallic materials and can effectively inactivate different microorganisms by direct contact. Compared with silver, copper is lower in cost and is also an essential trace element for various biological systems, and can play a role of a catalytic cofactor. Copper is the first solid material registered with the United States Environmental Protection Agency (USEPA) for antimicrobial properties and more than 350 copper alloys have been registered for antimicrobial activity against six different bacteria. Compared with metal surfaces, metal nanomaterials and metal oxides have the advantage of increasing the contact area of microorganisms with metals or metal oxides to obtain better antibacterial effect, but they are easily permeated into the environment, thereby causing secondary pollution such as generation of active oxygen and other health problems.
The preparation method of the copper oxide nano whisker surface, which is low in cost, simple in operation and capable of being prepared in a large area, is provided, and the copper oxide nano whisker is attached to the surface of metal copper, so that secondary pollution to the environment can be avoided. The method can control the morphological characteristics of the copper oxide nanowhiskers by adjusting anodic oxidation voltage, time, electrolyte components and the like, thereby increasing the specific surface area of the copper oxide nanowhiskers to obtain higher antibacterial property, and can be used for surfaces needing direct contact in hospitals and other environments, such as handrails, door handles, elevator buttons and the like, so as to prevent and reduce bacterial infection.
Disclosure of Invention
The antimicrobial properties of copper and its oxides are achieved mainly by direct interaction between the surface of the material and the bacteria, causing its film to break, also known as "contact sterilization". This mechanism of antimicrobial properties highlights the importance of direct contact of microorganisms with the surface of the material for effective eradication and inactivation of bacteria. In the last decade, different copper and copper oxide nanomaterials have been developed to improve their antibacterial activity, and the unique small size of such nanomaterials provides a large specific surface area, thereby maximizing the direct contact area of microorganisms with the material and improving the antibacterial effect. The main methods for directly generating the nano-scale structure on the metal surface include vapor deposition, laser processing, chemical etching and the like, but the methods generally have the disadvantages of complex flow, high operation difficulty and high cost. In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing a copper oxide nanowhisker structure directly attached to the surface of metallic copper, which is simple in operation, low in cost and capable of realizing large-area preparation. The specific surface area of the copper oxide nano whisker structure can be controlled by adjusting parameters such as anodic oxidation voltage, time, electrolyte components and the like, so that the sterilization effect of the copper oxide nano whisker structure is improved.
In order to achieve the above objects and other related objects, the present invention provides a preparation method comprising the steps of:
1) selecting a cathode electrode;
2) preparing a copper oxide nano whisker structure on the metal copper substrate, and selecting the components and the content of an electrolyte;
3) preparing a copper oxide nano whisker structure on the metal copper substrate, and selecting anodic oxidation time and voltage;
4) preparing a copper oxide nano whisker structure on a metal copper substrate by using the cathode electrode, the electrolyte and the experimental parameters selected in the steps 1), 2) and 3).
As a preferable scheme of the method for preparing the copper oxide nanowhisker structure of the present invention, the cathode electrode selected in step 1) mainly has a graphite electrode and a platinum sheet electrode.
As a preferable embodiment of the method for preparing the copper oxide nanowhisker structure of the present invention, the electrolyte selected in step 2) should be a medium strong acid or a weak acid.
As a preferable embodiment of the method for preparing a copper oxide nanowhisker structure of the present invention, the anodization voltage selected in step 3) should be 60V or less.
As a preferable embodiment of the method for preparing the copper oxide nanowhisker structure of the present invention, the anodic oxidation time selected in the step 3) should be 1 hour or less.
As a preferable embodiment of the method for preparing the copper oxide nanowhisker structure of the present invention, the step 4) further comprises the steps of:
4-1) preparing electrolyte according to the components and the content of the electrolyte selected in the step 2) and fully stirring the electrolyte;
4-2) respectively connecting the metal copper and the cathode electrode selected in the step 1) with the positive electrode and the negative electrode of direct current and immersing the metal copper and the cathode electrode in electrolyte;
4-3) preparing the copper oxide nano whisker structure according to the anodic oxidation time and voltage selected in the step 3).
As a preferable scheme of the preparation method of the copper oxide nanowhisker structure of the present invention, in the step 4-2), a beaker is selected as a reaction vessel while the distance between the anode and the cathode should be controlled.
As a preferable scheme of the preparation method of the copper oxide nanowhisker structure of the present invention, in the step 4-3) preparation process, the reaction temperature should be controlled and the electrolyte should be stirred in real time.
In addition, the morphology of the copper oxide nano whisker material can be regulated and controlled by adjusting parameters such as electrolyte components, anodic oxidation time, voltage, reaction temperature and the like, so that the copper oxide nano whisker material with the optimal sterilization effect can be obtained.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a copper oxide nanowhisker structure by an anodic oxidation method.
Figure 2 is a topographical view of a copper oxide nanowhisker structure taken with a scanning electron microscope.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that the examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
In the embodiment of the invention, the raw materials and equipment are commercially available and the purity is analytically pure or higher unless otherwise specified; in particular, the adopted oxalic acid is a commercial product, and the purity is analytical purity. The adopted metal copper foil is a commercial product, and the purity is industrial grade. The platinum sheet electrode, the direct current power supply, the constant temperature reaction bath, the beaker and the like are all commercial products.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
(1) Firstly, cutting a metal copper foil into a size similar to that of a platinum sheet electrode, flattening, then respectively placing the sample in acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic cleaning for 15min, and drying for later use. The surface of the pretreated sample is smooth and clean without dirt.
(2) An oxalic acid solution is adopted as electrolyte, wherein the content of oxalic acid is 0.3 mol/L; 5.4g of oxalic acid solid was dissolved in 200ml of deionized water and stirred well.
(3) As shown in figure 1, a 250ml beaker is used as a reaction vessel, a direct-current voltage-stabilizing and current-stabilizing power supply is used for supplying power, an anode is connected with a pretreated metal copper foil, a cathode is connected with a platinum sheet electrode with the area similar to that of the copper foil, the two electrodes are opposite, the distance between the two electrodes is controlled to be about 6cm, a magnetic stirrer is started for stirring, and electrolysis is carried out for 15min at the voltage of 40V. The temperature of the electrolyte was controlled at 5 ℃ throughout the experiment using a constant temperature reaction bath.
(4) The electrolyzed sample was ultrasonically cleaned in acetone and deionized water for 3min and dried.
(5) The sample was observed by a scanning electron microscope, and the copper oxide nanowhisker structure was found on the surface, as shown in FIG. 2.
Claims (5)
1. A preparation method of a copper oxide nano whisker structure is characterized by comprising the following steps: the preparation method comprises the following steps:
1) selecting a cathode electrode;
2) preparing a copper oxide nano whisker structure on the metal copper substrate, and selecting the components and the content of an electrolyte;
3) preparing a copper oxide nano whisker structure on the metal copper substrate, and selecting anodic oxidation time and voltage;
4) preparing a copper oxide nanowhisker structure on a metal copper substrate by using the substrate, the electrolyte and the experimental parameters selected in the steps 1), 2) and 3), wherein the preparation process comprises the following steps:
4-1) preparing electrolyte according to the components and the content of the electrolyte selected in the step 2) and fully stirring the electrolyte;
4-2) respectively connecting the metal copper and the cathode electrode selected in the step 1) with the positive electrode and the negative electrode of direct current and immersing the metal copper and the cathode electrode in electrolyte;
4-3) preparing the copper oxide nano whisker structure according to the anodic oxidation time and voltage selected in the step 3).
2. The method of claim 1, wherein the cathode electrode is selected in step 1) to be a material less noble than copper metal, typically a graphite electrode or a platinum sheet electrode.
3. The method of claim 1, wherein the electrolyte in step 2) is selected to react with copper metal under power-on conditions, wherein the electrolyte is a medium or weak acid, and the electrolyte is selected to be a strong acid or a weak acid, which may cause the formation of the copper oxide nanowhisker structure.
4. The method of claim 1, wherein the oxidation voltage in step 3) is selected to be too high to cause too severe a reaction and thus to prevent formation of the copper oxide nanowhisker structure, and is typically below 60V.
5. The method of claim 1, wherein the oxidation time in step 3) is selected to be too long to form the copper oxide nanowhisker structure, and is typically less than 1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010577160.8A CN111807314A (en) | 2020-06-23 | 2020-06-23 | Copper oxide nano whisker material with rapid sterilization and large contact surface |
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| CN202010577160.8A CN111807314A (en) | 2020-06-23 | 2020-06-23 | Copper oxide nano whisker material with rapid sterilization and large contact surface |
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| CN111807314A true CN111807314A (en) | 2020-10-23 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3716122A1 (en) * | 1987-05-14 | 1988-12-01 | Battelle Institut E V | Method of incorporating whiskers in a metallic matrix |
| RU2464224C1 (en) * | 2011-05-20 | 2012-10-20 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Method of producing copper oxide nanowhisker structures |
| CN103764544A (en) * | 2011-07-26 | 2014-04-30 | 1D材料有限责任公司 | Nanostructured battery active materials and methods of producing same |
| RU2574629C1 (en) * | 2014-07-23 | 2016-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" | Method for obtaining copper-containing material in form of metal substrate with copper microparticles applied on it |
| CN106835219A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
-
2020
- 2020-06-23 CN CN202010577160.8A patent/CN111807314A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3716122A1 (en) * | 1987-05-14 | 1988-12-01 | Battelle Institut E V | Method of incorporating whiskers in a metallic matrix |
| RU2464224C1 (en) * | 2011-05-20 | 2012-10-20 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Method of producing copper oxide nanowhisker structures |
| CN103764544A (en) * | 2011-07-26 | 2014-04-30 | 1D材料有限责任公司 | Nanostructured battery active materials and methods of producing same |
| RU2574629C1 (en) * | 2014-07-23 | 2016-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" | Method for obtaining copper-containing material in form of metal substrate with copper microparticles applied on it |
| CN106835219A (en) * | 2017-01-19 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李素等: "电化学方法制备氧化铜晶须", 《化工学报》, vol. 61, no. 1, 30 November 2010 (2010-11-30), pages 112 - 115 * |
| 蒋婷婷: "形貌可控纳米氧化铜的制备及其性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 February 2017 (2017-02-15), pages 56 - 68 * |
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