CN103421352B - 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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- CN103421352B CN103421352B CN201210161196.3A CN201210161196A CN103421352B CN 103421352 B CN103421352 B CN 103421352B CN 201210161196 A CN201210161196 A CN 201210161196A CN 103421352 B CN103421352 B CN 103421352B
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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
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- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a preparation method of a composite material with surfaces of cuprous oxide coated by copper oxide. 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; wherein the regulated temperature range is 70 DEG C-90 DEG C, the pH value range is 8-10, the coating reaction time is 0.5-2h; after the coating reaction, the reaction product is cooled to the room temperature, filtered, washed and dried, the cuprous oxide powder coated with the copper oxide is produced, the granularity of the cuprous oxide powder is 50nm-10mum, and the thickness of the copper oxide coating the cuprous oxide surface is 5nm-50nm. 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 matrix material of the coated cupric oxide in a kind of Red copper oxide surface 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 in the process of human development oceanic resources, run into the great difficult problem of biodeterioration, 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 hull bottom face more coarse, thereby the resistance while producing ship's navigation, consume more fuel, 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 marine biofouling method effective and that generally adopt from being brushing antifouling paint.Antifouling paint is mainly 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 for antifouling paint in Red copper oxide, 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; US Patent No. 5707438 has proposed a kind of method of pyrogenic process that adopts and has dissolved cupric oxide protective layer at the Surface Oxygen of Red copper oxide; thereby prevent that the aerial continuation of Red copper oxide has been oxidized and has controlled the dissolution rate of Red copper oxide in seawater; the method of the pyrogenic process using 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 matrix material of the coated cupric oxide in a kind of Red copper oxide surface and preparation method thereof, it can realize the even thickness of coated cupric oxide.
Matrix material providing the coated cupric oxide in a kind of Red copper oxide surface and preparation method thereof is provided, and 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 the coated cupric oxide in a kind of Red copper oxide surface comprises step: 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 and in suspension liquid, carry out coating reaction, in coating reaction process, keep pH value constant, to form resultant of reaction, described resultant of reaction is the matrix material of the coated cupric oxide in Red copper oxide surface, and wherein, described specified temperature scope is 70 ℃～90 ℃, pH value scope is 8～10, and the time of coating reaction is 0.5～2h; After coating reaction, be cooled to room temperature; Resultant of reaction is filtered, washs, is dried, make the coated Red copper oxide powder of cupric oxide, wherein, 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.
In order to realize above-mentioned purpose of the present invention, in second aspect, the invention provides the matrix material of the coated cupric oxide in a kind of Red copper oxide surface, it is according to preparation method's preparation of the matrix material of the described coated cupric oxide in Red copper oxide surface of the present invention's the first invention.
Beneficial effect of the present invention is as follows.
Method than existing employing pyrogenic process dissolves one deck cupric oxide at Red copper oxide Surface Oxygen, and the present invention adopts, and to be that solution reaction method is carried out surface coated, can obtain comparatively uniform cupric oxide coating layer.
Method than existing employing pyrogenic process dissolves one deck cupric oxide at Red copper oxide Surface Oxygen, and the present invention adopts is that solution reaction method is carried out surface and is coated, and the thickness of coating layer can be controlled according to the addition of coating.
The matrix material of the coated cupric oxide in Red copper oxide surface obtaining by the present invention, can prevent that Red copper oxide is transformed into cupric oxide in air on the one hand in use, thereby lose 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
First illustrate below according to the preparation method of the matrix material of the coated cupric oxide in Red copper oxide of the present invention surface.
Preparation method according to the matrix material of the coated cupric oxide in Red copper oxide of the present invention surface, comprises step: 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 and in suspension liquid, carry out coating reaction, in coating reaction process, keep pH value constant, to form resultant of reaction, described resultant of reaction is the matrix material of the coated cupric oxide in Red copper oxide surface; After coating reaction, be cooled to room temperature; Resultant of reaction is filtered, washs, is dried.
In the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to the present invention surface, 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.
In the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to the present invention surface, 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.
In the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to the present invention surface, 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.
In the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to the present invention surface, 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.
In the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to the present invention surface, preferably, in described matrix material, the thickness of the surface coated cupric oxide of Red copper oxide is 5nm～50nm.
The preparation method who is coated the matrix material of cupric oxide on Red copper oxide according to the present invention surface preferably, adopts ultrasonic dispersion when preparing suspension liquid.
In the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to the present invention surface, preferably, in being joined to suspension liquid, copper salt solution, sodium hydroxide solution carry out being added with magnetic agitation in coating reaction process.More preferably, the speed of magnetic agitation is 200～500rpm.
In the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to the present invention surface, preferably, temperature when dry is 50 ℃.
Secondly explanation is according to the preparation method's of the matrix material of the coated cupric oxide in Red copper oxide of the present invention surface embodiment.
Embodiment 1
The first step: add the deionized water of 100ml in round-bottomed flask, add 0.005g Sodium dodecylbenzene sulfonate, add the Red copper oxide powder of 5g50nm 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, under 200rpm condition, suspension liquid is heated to 70 ℃, pH value is adjusted to 8, with peristaltic pump, the sodium hydroxide solution of the copper-bath 25ml of 10g/L and 4g/L is slowly added drop-wise in suspension liquid, in coating reaction process, keep pH value constant, the coating reaction time is 0.5h, continues to stir until be cooled to room temperature, then filter washing and dry at 50 ℃, making the coated Red copper oxide powder of cupric oxide.
Embodiment 2
The first step: add the deionized water of 100ml in round-bottomed flask, add 0.05g sodium lauryl sulphate, add 27.5g500nm 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, under 350rpm condition, suspension liquid is heated to 80 ℃, pH value is adjusted to 9, with peristaltic pump, the sodium hydroxide solution of the copper-bath 75ml of 55g/L and 12g/L is slowly added drop-wise in suspension liquid, in coating reaction process, keep pH value constant, the coating reaction time is 1h, continues to stir until be cooled to room temperature, then filter washing and dry at 50 ℃, making the coated Red copper oxide powder of cupric oxide.
Embodiment 3
The first step: add the deionized water of 100ml in round-bottomed flask, add 0.0275g Sodium hexametaphosphate 99, add the Red copper oxide powder of 50g10 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, under 500rpm condition, suspension liquid is heated to 90 ℃, pH value is adjusted to 10, with peristaltic pump, the sodium hydroxide solution of the copper-bath 125ml of 100g/L and 16g/L is slowly added drop-wise in suspension liquid, in coating reaction process, keep pH value constant, the coating reaction time is 2h, continues to stir until be cooled to room temperature, then filter washing and dry at 50 ℃, making the coated Red copper oxide powder of cupric oxide.
The detected result of embodiment 1-3 is finally described.
The detected result method of embodiment 1-3 is focused beam ion technology.
Detected result is that the thickness of coated cupric oxide is respectively on Red copper oxide powder: embodiment 1 is 5nm, and embodiment 2 is 25nm, and embodiment 3 is 50nm.
Finally illustrate according to the matrix material of the coated cupric oxide in Red copper oxide of the present invention surface.
According to the matrix material of the coated cupric oxide in Red copper oxide of the present invention surface, be to obtain according to aforementioned preparation method.
According to Red copper oxide of the present invention surface, be coated in 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 (7)
1. Red copper oxide surface is coated a preparation method for the matrix material of cupric oxide, comprises step:
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 and in suspension liquid, carry out coating reaction, in coating reaction process, keep pH value constant, to form resultant of reaction, described resultant of reaction is the matrix material of the coated cupric oxide in Red copper oxide surface, wherein said specified temperature scope is 70 ℃～90 ℃, and pH value scope is 8～10, and the time of coating reaction is 0.5～2h;
After coating reaction, be cooled to room temperature;
Resultant of reaction is filtered, washs, is dried, make the coated Red copper oxide powder of cupric oxide, wherein, 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.
2. the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to claim 1 surface, 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. the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to claim 1 surface, is characterized in that, dispersion agent is selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or Sodium hexametaphosphate 99 or their mixture.
4. the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to claim 3 surface, is characterized in that, the concentration of dispersion agent is 0.05g/L～0.5g/L.
5. the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to claim 1 surface, is characterized in that, described copper salt solution is copper-bath.
6. Red copper oxide according to claim 5 surface is coated 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.
7. the preparation method of the matrix material of the coated cupric oxide in Red copper oxide according to claim 1 surface, 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 coating reaction process.
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 |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210161196.3A 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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| CN103421352A CN103421352A (en) | 2013-12-04 |
| CN103421352B true CN103421352B (en) | 2014-11-19 |
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| 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 |
| 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 |
| CN106929934B (en) * | 2017-03-15 | 2018-12-28 | 赵宝勤 | A kind of preparation method of composite Nano algicide-antifoulant |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN101560320B (en) * | 2009-05-14 | 2011-01-05 | 浙江理工大学 | Preparation method of composite material coating polymer microsphere surface with copper oxide |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 (2)
| Title |
|---|
| 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》.2010,(第9期),第B020-29页. * |
| 贵金属纳米材料的电化学合成和物性研究;洪勋;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20100915(第9期);第B020-29页 * |
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| WO2013174250A1 (en) | 2013-11-28 |
| CN103421352A (en) | 2013-12-04 |
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