CN103421352A - Composite material with surfaces of cuprous oxide coated by copper oxide and preparation method - Google Patents
Composite material with surfaces of cuprous oxide coated by copper oxide and preparation method Download PDFInfo
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- CN103421352A CN103421352A CN2012101611963A CN201210161196A CN103421352A CN 103421352 A CN103421352 A CN 103421352A CN 2012101611963 A CN2012101611963 A CN 2012101611963A CN 201210161196 A CN201210161196 A CN 201210161196A CN 103421352 A CN103421352 A CN 103421352A
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- red copper
- copper oxide
- preparation
- matrix material
- oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
Abstract
The invention provides a composite material with surfaces of cuprous oxide coated by copper oxide and a preparation method. The preparation method comprises steps: cuprous oxide powder is dispersed in deionized water containing dispersants to prepare a suspension; a copper salt solution and a sodium hydroxide solution are added into the suspension and subjected to a coating reaction at the specified temperature and at the specified pH value, the pH value is constant during the coating reaction process, a reaction product is formed, the reaction product is a composite material with surfaces of cuprous oxide coated by copper oxide; after the coating reaction, the reaction product is cooled to the room temperature, filtered, washed and dried. The composite material is prepared through the preparation method. Through the preparation method, relatively-uniform copper oxide coating layers can be obtained, and the thickness of the coating layers is controllable.
Description
Technical field
The present invention relates to a kind of synthetic materials and preparation method thereof, relate in particular to a kind of Red copper oxide surface and coat matrix material of cupric oxide and preparation method thereof.
Background technology
Abundant natural resources has been brought for the mankind in the ocean of the length and breadth of land, yet run into the great difficult problem of biodeterioration in the process of human development oceanic resources, marine fouling organism is attached on the various facilities waterborne such as ship, offshore drilling platform, buoy, mariculture facility, hydrospace detection instrument, can cause the increase of ship weight, make the hull bottom face more coarse, thereby the resistance while producing ship's navigation, consume more fuel, the infringement power machine, shorten the work-ing life that depressed place is repaiied the timed interval and shortened boats and ships, thereby bring huge financial loss.Up to now, prevent that the effective and method that generally adopt of marine biofouling from being the brushing antifouling paint.Antifouling paint mainly is comprised of institutes such as resin, stain control agent, color stuffing and auxiliary agents, and what wherein play a decisive role is stain control agent.Red copper oxide is to use one of stain control agent with the longest history, has the advantages such as safe, inexpensive.But also there is certain limitation in Red copper oxide for antifouling paint, and first Red copper oxide is unstable in air, easily oxidized; It two is the rate of release of cupric ion in seawater very fast (5.4 μ g/ml), and the work-ing life of Red copper oxide antifouling varnish is shorter.
For improving these shortcomings of Red copper oxide; U.S. Pat 5707438 has proposed a kind of method of pyrogenic process that adopts and has dissolved the cupric oxide protective layer at the Surface Oxygen of Red copper oxide; thereby prevent the aerial continuation oxidation of Red copper oxide and controlled the dissolution rate of Red copper oxide in seawater; the method of the pyrogenic process used due to this patent, can cause the inequality of oxidation and the uncontrollability of oxidated layer thickness.
Summary of the invention
In view of the problem that prior art exists, the object of the present invention is to provide a kind of Red copper oxide surface to coat matrix material of cupric oxide and preparation method thereof, it can realize the even thickness of coated cupric oxide.
Another object of the present invention is to provide a kind of Red copper oxide surface to coat matrix material of cupric oxide and preparation method thereof, its thickness that can realize coated cupric oxide is controlled.
In order to realize above-mentioned purpose of the present invention, in first aspect, the preparation method who the invention provides the matrix material of a kind of Red copper oxide surface coating cupric oxide comprises step: the Red copper oxide powder is dispersed in the deionized water containing dispersion agent, to prepare suspension liquid; Under specified temperature, regulation pH value, copper salt solution, sodium hydroxide solution are joined in suspension liquid and carry out coating reaction, in the coating reaction process, keep the pH value constant, to form resultant of reaction, described resultant of reaction is the matrix material that the Red copper oxide surface coats cupric oxide; After coating reaction, be cooled to room temperature; To resultant of reaction filtered, washed, drying.
In order to realize above-mentioned purpose of the present invention, in second aspect, the invention provides the matrix material that a kind of Red copper oxide surface coats cupric oxide, it coats preparation method's preparation of the matrix material of cupric oxide according to the present invention's described Red copper oxide of the first invention surface.
Beneficial effect of the present invention is as follows.
Method than existing employing pyrogenic process dissolves one deck cupric oxide at the Red copper oxide Surface Oxygen, and what the present invention adopted is that the solution reaction method is carried out the surface coating, can obtain cupric oxide coating layer comparatively uniformly.
Method than existing employing pyrogenic process dissolves one deck cupric oxide at the Red copper oxide Surface Oxygen, and what the present invention adopted is that the solution reaction method is carried out the surface coating, and the thickness of coating layer can be controlled according to the addition of coating.
The Red copper oxide surface obtained by the present invention coats the matrix material of cupric oxide, can prevent that Red copper oxide is transformed into cupric oxide in air on the one hand in use, thereby loses anti-pollution function; Can control on the other hand the rate of release of Red copper oxide in seawater, the waste of less Red copper oxide with and the pollution to water surrounding to the deposition of coastal waters, port and pier.
Embodiment
At first the preparation method who coats the matrix material of cupric oxide according to Red copper oxide of the present invention surface below is described.
Coat the preparation method of the matrix material of cupric oxide according to Red copper oxide of the present invention surface, comprise step: the Red copper oxide powder is dispersed in the deionized water containing dispersion agent, to prepare suspension liquid; Under specified temperature, regulation pH value, copper salt solution, sodium hydroxide solution are joined in suspension liquid and carry out coating reaction, in the coating reaction process, keep the pH value constant, to form resultant of reaction, described resultant of reaction is the matrix material that the Red copper oxide surface coats cupric oxide; After coating reaction, be cooled to room temperature; To resultant of reaction filtered, washed, drying.
On Red copper oxide according to the present invention surface, coat in the preparation method of matrix material of cupric oxide, preferably, when preparing suspension liquid, the granularity of Red copper oxide powder is 50nm ~ 10 μ m; The concentration of Red copper oxide is 50g/L ~ 500g/L.
On Red copper oxide according to the present invention surface, coat in the preparation method of matrix material of cupric oxide, preferably, dispersion agent is selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or Sodium hexametaphosphate 99 or their mixture.More preferably, the concentration of dispersion agent is 0.05g/L ~ 0.5g/L.
On Red copper oxide according to the present invention surface, coat in the preparation method of matrix material of cupric oxide, preferably, described specified temperature scope is 70 ℃ ~ 90 ℃, and pH value scope is 8 ~ 10, and the time of coating reaction is 0.5 ~ 2h.
On Red copper oxide according to the present invention surface, coat in the preparation method of matrix material of cupric oxide, preferably, described copper salt solution is copper-bath.More preferably, the concentration of copper-bath is 10g/L ~ 100g/L, and in copper-bath, the amount of contained copper sulfate is 5% ~ 25% of Red copper oxide powder quality.Preferably, the concentration of sodium hydroxide solution is 4g/L ~ 16g/L.
On Red copper oxide according to the present invention surface, coat in the preparation method of matrix material of cupric oxide, preferably, in described matrix material, the thickness of the surface coated cupric oxide of Red copper oxide is 5nm ~ 50nm.
Coat the preparation method of the matrix material of cupric oxide on Red copper oxide according to the present invention surface, preferably, adopt ultrasonic dispersion when preparing suspension liquid.
Coat in the preparation method of matrix material of cupric oxide on Red copper oxide according to the present invention surface, preferably, carry out being added with magnetic agitation in the coating reaction process in copper salt solution, sodium hydroxide solution are joined to suspension liquid.More preferably, the speed of magnetic agitation is 200 ~ 500rpm.
On Red copper oxide according to the present invention surface, coat in the preparation method of matrix material of cupric oxide, preferably, temperature when dry is 50 ℃.
Secondly explanation is according to the preparation method's of the matrix material of Red copper oxide of the present invention surface coating cupric oxide embodiment.
Embodiment 1
The first step: add the deionized water of 100ml in round-bottomed flask, add the 0.005g Sodium dodecylbenzene sulfonate, add the Red copper oxide powder of 5g 50nm after stirring and dissolving, ultrasonic dispersion 15min makes the Red copper oxide suspension liquid of stable dispersion;
Second step: above-mentioned suspension liquid is moved in magnetic stirring apparatus, suspension liquid is heated to 70 ℃ under the 200rpm condition, the pH value is adjusted to 8, with peristaltic pump, slowly be added drop-wise to the sodium hydroxide solution of the copper-bath 25ml of 10g/L and 4g/L in suspension liquid, in the coating reaction process, keep the pH value constant, the coating reaction time is 0.5h, continues to stir until be cooled to room temperature, then filter washing and dry under 50 ℃, making the Red copper oxide powder that cupric oxide coats.
Embodiment 2
The first step: add the deionized water of 100ml in round-bottomed flask, add the 0.05g sodium lauryl sulphate, add 27.5g 500nm Red copper oxide powder after stirring and dissolving, ultrasonic dispersion 15min makes the Red copper oxide suspension liquid of stable dispersion;
Second step: above-mentioned suspension liquid is moved in magnetic stirring apparatus, suspension liquid is heated to 80 ℃ under the 350rpm condition, the pH value is adjusted to 9, with peristaltic pump, slowly be added drop-wise to the sodium hydroxide solution of the copper-bath 75ml of 55g/L and 12g/L in suspension liquid, in the coating reaction process, keep the pH value constant, the coating reaction time is 1h, continues to stir until be cooled to room temperature, then filter washing and dry under 50 ℃, making the Red copper oxide powder that cupric oxide coats.
Embodiment 3
The first step: add the deionized water of 100ml in round-bottomed flask, add the 0.0275g Sodium hexametaphosphate 99, add the Red copper oxide powder of 50g 10 μ m after stirring and dissolving, ultrasonic dispersion 15min makes the Red copper oxide suspension liquid of stable dispersion;
Second step: above-mentioned suspension liquid is moved in magnetic stirring apparatus, suspension liquid is heated to 90 ℃ under the 500rpm condition, the pH value is adjusted to 10, with peristaltic pump, slowly be added drop-wise to the sodium hydroxide solution of the copper-bath 125ml of 100g/L and 16g/L in suspension liquid, in the coating reaction process, keep the pH value constant, the coating reaction time is 2h, continues to stir until be cooled to room temperature, then filter washing and dry under 50 ℃, making the Red copper oxide powder that cupric oxide coats.
The detected result of embodiment 1-3 finally is described.
The detected result method of embodiment 1-3 is the focused beam ion technology.
The thickness that detected result is the cupric oxide that coats on the Red copper oxide powder is respectively: embodiment 1 is 5nm, and embodiment 2 is 25nm, and embodiment 3 is 50nm.
The matrix material that coats cupric oxide according to Red copper oxide of the present invention surface finally is described.
The matrix material that coats cupric oxide according to Red copper oxide of the present invention surface is to obtain according to aforementioned preparation method.
According to Red copper oxide of the present invention surface, coating the matrix material of cupric oxide, preferably, the granularity of Red copper oxide powder is 50nm ~ 10 μ m, and the thickness of the surface coated cupric oxide of Red copper oxide is 5nm ~ 50nm.
Claims (10)
1. Red copper oxide surface coats the preparation method of the matrix material of cupric oxide, comprises step:
The Red copper oxide powder is dispersed in the deionized water containing dispersion agent, to prepare suspension liquid;
Under specified temperature, regulation pH value, copper salt solution, sodium hydroxide solution are joined in suspension liquid and carry out coating reaction, in the coating reaction process, keep the pH value constant, to form resultant of reaction, described resultant of reaction is the matrix material that the Red copper oxide surface coats cupric oxide;
After coating reaction, be cooled to room temperature;
To resultant of reaction filtered, washed, drying.
2. Red copper oxide according to claim 1 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, when preparing suspension liquid, the granularity of Red copper oxide powder is 50nm ~ 10 μ m; The concentration of Red copper oxide is 50g/L ~ 500g/L.
3. Red copper oxide according to claim 1 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, dispersion agent is selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or Sodium hexametaphosphate 99 or their mixture.
4. Red copper oxide according to claim 3 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, the concentration of dispersion agent is 0.05g/L ~ 0.5g/L.
5. Red copper oxide according to claim 1 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, described specified temperature scope is 70 ℃ ~ 90 ℃, and pH value scope is 8 ~ 10, and the time of coating reaction is 0.5 ~ 2h.
6. Red copper oxide according to claim 1 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, described copper salt solution is copper-bath.
7. Red copper oxide according to claim 6 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, the concentration of copper-bath is 10g/L ~ 100g/L, in copper-bath, the amount of contained copper sulfate is 5% ~ 25% of Red copper oxide powder quality, and the concentration of sodium hydroxide solution is 4g/L ~ 16g/L.
8. Red copper oxide according to claim 1 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, in described matrix material, the granularity of Red copper oxide powder is 50nm ~ 10 μ m, and the thickness of the surface coated cupric oxide of Red copper oxide is 5nm ~ 50nm.
9. Red copper oxide according to claim 1 surface coats the preparation method of the matrix material of cupric oxide, it is characterized in that, adopts ultrasonic dispersion when preparing suspension liquid; In being joined to suspension liquid, copper salt solution, sodium hydroxide solution carry out being added with magnetic agitation in the coating reaction process.
10. Red copper oxide surface coats the matrix material of cupric oxide, and it coats preparation method's preparation of the matrix material of cupric oxide according to the described Red copper oxide of any one in claim 1-9 surface.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210161196.3A CN103421352B (en) | 2012-05-21 | 2012-05-21 | Composite material with surfaces of cuprous oxide coated by copper oxide and preparation method |
| PCT/CN2013/075970 WO2013174250A1 (en) | 2012-05-21 | 2013-05-21 | Composite of cuprous oxide surface-coated with copper oxide and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210161196.3A CN103421352B (en) | 2012-05-21 | 2012-05-21 | Composite material with surfaces of cuprous oxide coated by copper oxide and preparation method |
Publications (2)
| Publication Number | Publication Date |
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| CN103421352A true CN103421352A (en) | 2013-12-04 |
| CN103421352B CN103421352B (en) | 2014-11-19 |
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| CN201210161196.3A Active CN103421352B (en) | 2012-05-21 | 2012-05-21 | Composite material with surfaces of cuprous oxide coated by copper oxide and preparation method |
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| CN (1) | CN103421352B (en) |
| WO (1) | WO2013174250A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105116030A (en) * | 2015-07-27 | 2015-12-02 | 中国海洋大学 | Cu2O@CuO semi-core-shell structure nano composite material and preparation method therefor |
| CN106041120A (en) * | 2016-06-28 | 2016-10-26 | 昆明理工大学 | Preparation method of copper/cuprous oxide core-shell structure nanometer material |
| CN106929934A (en) * | 2017-03-15 | 2017-07-07 | 赵宝勤 | A kind of preparation method of composite Nano algicide-antifoulant |
| CN109926048A (en) * | 2019-04-09 | 2019-06-25 | 大连理工大学 | A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application |
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| CN101560320A (en) * | 2009-05-14 | 2009-10-21 | 浙江理工大学 | Composite material coating polymer microsphere surface with copper oxide, and preparation method thereof |
| CN102350499A (en) * | 2011-09-28 | 2012-02-15 | 河北工业大学 | Cu/Cu2O core-shell composite microsphere and preparation method thereof |
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| US5707438A (en) * | 1996-02-21 | 1998-01-13 | American Chemet Corporation | Composite cuprous oxide powder |
| JP4197151B2 (en) * | 2003-11-27 | 2008-12-17 | 三井金属鉱業株式会社 | Two-layer coated copper powder, method for producing the two-layer coated copper powder, and conductive paste using the two-layer coated copper powder |
| JP2009197221A (en) * | 2008-01-24 | 2009-09-03 | Nippon Chem Ind Co Ltd | Powder coated with cuprous oxide and manufacturing method thereof |
| JP2011042559A (en) * | 2009-07-22 | 2011-03-03 | Nippon Chem Ind Co Ltd | Particle coated with cuprous oxide and method for producing the same, and antifouling coating material containing the particle coated with cuprous oxide |
| CN102250499B (en) * | 2011-05-16 | 2013-11-06 | 大连海事大学 | Preparation method of cuprous oxide coated and treated by rosin |
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2012
- 2012-05-21 CN CN201210161196.3A patent/CN103421352B/en active Active
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2013
- 2013-05-21 WO PCT/CN2013/075970 patent/WO2013174250A1/en active Application Filing
Patent Citations (2)
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| CN101560320A (en) * | 2009-05-14 | 2009-10-21 | 浙江理工大学 | Composite material coating polymer microsphere surface with copper oxide, and preparation method thereof |
| CN102350499A (en) * | 2011-09-28 | 2012-02-15 | 河北工业大学 | Cu/Cu2O core-shell composite microsphere and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 洪勋: "贵金属纳米材料的电化学合成和物性研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 9, 15 September 2010 (2010-09-15), pages 020 - 29 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105116030A (en) * | 2015-07-27 | 2015-12-02 | 中国海洋大学 | Cu2O@CuO semi-core-shell structure nano composite material and preparation method therefor |
| CN105116030B (en) * | 2015-07-27 | 2017-11-03 | 中国海洋大学 | A kind of Cu2Nuclear-shell structured nano-composite materials of O@CuO half and preparation method thereof |
| CN106041120A (en) * | 2016-06-28 | 2016-10-26 | 昆明理工大学 | Preparation method of copper/cuprous oxide core-shell structure nanometer material |
| CN106041120B (en) * | 2016-06-28 | 2018-05-25 | 昆明理工大学 | A kind of preparation method of copper/cuprous oxide core-shell structured nanomaterials |
| CN106929934A (en) * | 2017-03-15 | 2017-07-07 | 赵宝勤 | A kind of preparation method of composite Nano algicide-antifoulant |
| CN109926048A (en) * | 2019-04-09 | 2019-06-25 | 大连理工大学 | A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application |
| CN109926048B (en) * | 2019-04-09 | 2021-08-20 | 大连理工大学 | Single-component double-active-site Cu2O-CuO nano mixed phase structure copper oxide catalyst, preparation method and application |
Also Published As
| Publication number | Publication date |
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| CN103421352B (en) | 2014-11-19 |
| WO2013174250A1 (en) | 2013-11-28 |
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