CN107557718A - A kind of method for preparing inorganic nano material layer on flexible material surface - Google Patents
A kind of method for preparing inorganic nano material layer on flexible material surface Download PDFInfo
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- CN107557718A CN107557718A CN201610472145.0A CN201610472145A CN107557718A CN 107557718 A CN107557718 A CN 107557718A CN 201610472145 A CN201610472145 A CN 201610472145A CN 107557718 A CN107557718 A CN 107557718A
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Abstract
The present invention relates to a kind of method for preparing inorganic nano material layer on flexible material surface, including elder generation forms oxide layer in the surface spraying liquid metal of the flexible material, the step of then preparing inorganic nano material layer on the surface of the oxide layer.The present invention uses liquid metal oxidation film layer as flexible material and the cushion of inorganic nano material, solve the problems, such as to prepare inorganic nano material difficulty on flexible material surface well, and provide preparation method is simple, cost is low, may be implemented in that flexible base material surface is quick, prepares nanostructured on a large scale.
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of to prepare nothing on flexible material surface
The method of machine layer of nanomaterial, ZnO nano is prepared more particularly, on flexible material surface
The method of structure.
Background technology
Inorganic material has small-size effect, therefore tool has been widely used, such as battery, dredges
Water material etc.；Inorganic material is supported on flexible high molecular material surface, realizes organic and inorganic compound
Condensation material, there is obvious advantage in application field, still, prior art is difficult in flexibility
Polymer surface forms stable inorganic structure, and this just gives the application shape of inorganic nano material
Into obstacle, the application field of material is limited.
It is therefore proposed that a kind of method is to overcome inorganic material to be difficult to be formed in polymer surface
The problem of it is necessary.
The content of the invention
The purpose of the present invention is organic high for inorganic nano material present in prior art
Molecular flexibility material surface is not easy to be formed, and prepares the defects of difficult, there is provided one kind is in flexible material
The method that surface prepares inorganic nano material layer.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of method for preparing inorganic nano material layer on flexible material surface, including elder generation is described
The surface spraying liquid metal of flexible material forms oxide layer, then on the surface of the oxide layer
The step of preparing inorganic nano material layer.
Wherein, the liquid metal is selected from GaIn alloys, GaInSn alloys, GaInZn alloys
Or one kind in GaInBi alloys.The fusing point of these liquid metals is moderate, suitably at normal temperatures
Sprayed, it is easy to operate；And oxide-film is easily formed, contribute to the attachment of inorganic material.
Present invention preferably employs GaIn alloys, most preferably use Ga and In weight ratio as (5-20)：
1 GaIn alloys.The alloy of such a proportioning has low melting point property, contributes to cold spraying
Experiment, and it is particularly suitable for the formation of inorganic nanostructures (especially ZnO nano-structure).
The present invention in specific application, can use Ga and In weight ratio as 5:1 or 10:1 or 15:1
Or 20:1 GaIn alloys, Ga and In weight ratio is most preferably used as 10:1 alloy.
Can use high-pressure injection rifle commonly used in the art when spraying liquid metal, spray pressure with
8-12 atmospheric pressure (preferably 10 atmospheric pressure) is advisable.The method of the present invention both can be in flexible material
The one side of material is sprayed, and can also be sprayed on two sides.
Preferably, the thickness of liquid-metal layer is controlled to be no more than 100 μm in spraying process,
Such a coating layer thickness has the high advantage of adhesion, contributes to the combination of coating and substrate, prepares
Obtain the material of high quality.
Before the present invention prepares inorganic nano material layer on flexible material, first spraying forms one layer
Liquid metal oxide layer, liquid metal are a kind of liquid that can be flowed in normal temperature, are had very high
Surface energy, after liquid metal is sprayed on into flexible material surface, liquid metal is easy to catch
The oxygen in air is obtained, forms oxide-film, the formation of oxide-film prevents further oxidation,
This oxide-film can form the center of crystal growth, contribute to inorganic nano material to be given birth to thereon
It is long, ultimately form stable inorganic nano material layer.
The material of inorganic nano material layer of the present invention can need to select to prepare according to specific,
Preparation method can use hydrothermal synthesis method, will form the flexible material of liquid metal oxide layer
It is soaked in inorganic nano material growth-promoting media, reacts certain time under certain temperature, you can.
Preferably, the material of inorganic nano material layer is selected from one in ZnO, or SnO to the present invention
Kind, preferably ZnO, i.e., method of the present invention is particularly suitable for preparing ZnO nano-structure.
Specifically, the operation of ZnO or SnO inorganic nano material layers is prepared on oxide-film
For：Salt containing Zn or Sn and hexamethylenetetramine is soluble in water, prepare growth-promoting media；By shape
Flexible material into oxide layer is dipped in the growth-promoting media, is reacted under the conditions of 80-120 DEG C
6-24h。
Preferably, by weight, Zn or Sn is contained dissolved with 0.65-0.8 parts in every 100 parts of water
Salt and 0.2-06 part hexamethylenetetramines.
Wherein, the salt containing Zn or Sn preferably is selected from zinc nitrate or nitric acid tin.
The condition of Hydrothermal Synthesiss of the present invention preferably reacts 10-14h at 80-100 DEG C, most preferably at 90 DEG C
React 12h.
Invention also provides a kind of side that ZnO nano-structure is prepared on flexible material surface
Method, comprise the following steps：
(1) GaIn liquid metal alloys are sprayed on to the surface of the flexible material, stood
1-5min forms oxide-film；
(2) by the hexamethylenetetramine of 0.2-0.6 parts by weight and the nitric acid of 0.65-0.8 parts by weight
Zinc is dissolved in 100 parts by weight water, obtains inorganic nano material growth-promoting media；
(3) flexible material of step (1) is soaked in the inorganic nano material growth-promoting media,
6-24h is reacted under the conditions of 80-120 DEG C to produce.
Preferably, Ga and In weight ratio is (5-20) in GaIn alloys:1；
Preferably, in step (3), 10-14h is reacted in 80-100 DEG C.
It is by irregular cycle ZnO to adopt this method the inorganic nano material layer being prepared
What nanostructured (being similar to petal-shaped) was formed, the thickness degree is 50-300nm, the ZnO
A diameter of 100-500nm of nanostructured.ZnO nano-structure has the property of morphology controllable,
The material being prepared is adopted this method to can be used for doing hydrophobic material either battery material.
The present invention is used as the flexible material dawn known to those skilled in the art of substrate, including but not
The one kind being confined in paper, cloth, high polymer material.Wherein, the high polymer material is optional
One kind from rubber, plastics, fiber.Specifically, the high polymer material can be poly-
Vinyl chloride (PVC) material, polythene material (PE), polypropylene (PP) material etc.；Institute
It is preferably printing paper to state paper；The material of the cloth may be selected from cotton, burlap, silk, woollen goods,
One or more in chemical fibre, blending.
The present invention also provides a kind of flexible material of carrying inorganic layer of nanomaterial, the flexibility simultaneously
Material is prepared by any one above-mentioned method.
The present invention uses liquid metal oxidation film layer as flexible material and inorganic nano material
Cushion, solve the problems, such as to prepare inorganic nano material difficulty on flexible material surface well,
And provide preparation method is simple, cost is low, may be implemented in flexible base material surface it is quick,
It is extensive to prepare nanostructured.
Brief description of the drawings
Fig. 1 is the printing paper (left hand view) containing nanostructured and is only coated with liquid metal painting
The photo of the printing paper (right part of flg) of layer；
Fig. 2 is printing paper marginal texture stereoscan photograph, is paper fiber in the circle of the rightmost side,
It is liquid metal intermediate layer in middle circle, is ZnO nano-structure in Far Left circle；
Fig. 3 is the boundary scan electron microscope of ZnO nano-structure prepared by printing paper surface；
Fig. 4 is the nano junction composition of homoepitaxial in ZnO nano-structure prepared by printing paper surface；
Fig. 5 is Fig. 4 enlarged drawing；
Fig. 6 is the boundary scan electron microscope of ZnO nano-structure prepared by design on fabric surface；
Fig. 7 is the nano junction composition of homoepitaxial in ZnO nano-structure prepared by design on fabric surface；
Fig. 8 is Fig. 7 enlarged drawing；
Fig. 9 is the nano junction composition of homoepitaxial in ZnO nano-structure prepared by PVC film surface；
Figure 10 is Fig. 9 enlarged drawing.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
A kind of method that ZnO nano-structure is prepared on paper, comprises the following steps：
1) common A4 printing papers are taken, GaIn liquid metals are sprayed in one side surface with spray gun,
Stand 5min；Ga and In weight ratio is 10 wherein in GaIn liquid metals:1.
2) 0.3g hexamethylenetetramines and 0.6g zinc nitrates are added in 100mL deionized waters, mixing
Uniformly, stir to transparent and produce growth-promoting media；
3) 95mL growth-promoting medias and printing paper are put into 100mL ptfe autoclave simultaneously
In, 90 DEG C of keeping temperature is reacted 12 hours in drying box, and sample, deionization are taken out after cooling
Water cleans three times, dries, produces.
The present embodiment step (1) forms the printing paper of oxide-film as shown in Fig. 1 right part of flg, step
(3) printing paper obtained is as shown in Fig. 1 left hand views；ZnO nano knot prepared by printing paper surface
Structure (similar petal-shaped) is as shown in Figure 2-5.
Embodiment 2
A kind of method for preparing ZnO nano-structure in design on fabric surface, the operating procedure of this method are same
Embodiment 1, differ only in the cloth that flexible material selects 10x10cm (material is blending).
The ZnO nano-structure (similar petal-shaped) that the present embodiment is prepared in design on fabric surface is such as Fig. 6-8
It is shown.
Embodiment 3
A kind of method for preparing ZnO nano-structure on PVC film surface, the operation step of this method
Suddenly with embodiment 1, the PVC film that flexible material selects 10x10cm is differed only in.
The ZnO nano-structure (similar petal-shaped) that the present embodiment is prepared on PVC film surface is such as
Shown in Fig. 9-10.
Although general explanation, embodiment and experiment are above used, to this hair
It is bright to have made detailed description, but on the basis of the present invention, it can be made some modifications or improvements,
This will be apparent to those skilled in the art.Therefore, without departing from spirit of the invention
On the basis of these modifications or improvements, belong to the scope of protection of present invention.
Claims (10)
1. a kind of method for preparing inorganic nano material layer on flexible material surface, its feature exist
In, including elder generation is in the surface spraying liquid metal formation oxide layer of the flexible material, Ran Hou
The surface of the oxide layer prepares the step of inorganic nano material layer.
2. according to the method for claim 1, it is characterised in that the liquid metal choosing
One kind from GaIn alloys, GaInSn alloys, GaInBi alloys or GaInZn alloys.
3. method according to claim 1 or 2, it is characterised in that the liquid gold
Belong to for GaIn alloys, preferably Ga and In weight ratio is (5-20)：1 GaIn alloys, enter
The preferred Ga and In weight ratio of one step is 10：1 GaIn alloys.
4. according to the method described in claim any one of 1-3, it is characterised in that spraying
Liquid metal thickness≤100 μm.
5. according to the method described in claim any one of 1-4, it is characterised in that aoxidizing
The surface of layer prepares the operation of inorganic nano material layer：
Salt containing Zn or Sn and hexamethylenetetramine is soluble in water, prepare growth-promoting media；By shape
Flexible material into oxide layer is dipped in the growth-promoting media, is reacted under the conditions of 80-120 DEG C
6-24h, produce.
6. according to the method for claim 5, it is characterised in that：By weight, often
Dissolved with the salt containing Zn or Sn described in 0.65-0.8 parts, the methine of 0.2-06 parts six in 100 parts of water
Tetramine；Preferably, the salt containing Zn or Sn is selected from zinc nitrate or nitric acid tin.
7. according to the method for claim 1, it is characterised in that comprise the following steps：
(1) GaIn liquid metal alloys are sprayed on to the surface of the flexible material, stood
1-5min forms oxide-film；
(2) by the hexamethylenetetramine of 0.2-0.6 parts by weight and the nitric acid of 0.65-0.8 parts by weight
Zinc is dissolved in 100 parts by weight water, obtains growth-promoting media；
(3) flexible material obtained by step (1) is soaked in the growth-promoting media, in 80-120 DEG C
Under the conditions of react 6-24h, produce；
Preferably, Ga and In weight ratio is (5-20) in GaIn alloys:1；
Preferably, in step (3), 10-14h is reacted in 80-100 DEG C.
8. according to the method described in claim any one of 1-7, it is characterised in that：It is described soft
The one kind of property material in paper, cloth, high polymer material；
Preferably, the paper is printing paper, and the high polymer material is polyethylene.
9. any one of claim 1-6 methods described or claim 8 methods described are prepared into
The flexible material of the carrying inorganic layer of nanomaterial arrived.
10. the flexibility for the carrying inorganic layer of nanomaterial that claim 7 methods described is prepared
Material, it is characterised in that：The inorganic nano material layer is by irregular cycle ZnO nano knot
It is configured to, the thickness degree is 50-300nm, a diameter of 100-500nm of the nanostructured.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108220924A (en) * | 2018-01-26 | 2018-06-29 | 中国科学院理化技术研究所 | A kind of preparation method of Copper thin film |
| CN108457079A (en) * | 2018-04-27 | 2018-08-28 | 中国科学院理化技术研究所 | A kind of liquid metal/carbon fibre composite and its preparation method and application |
| CN109763109A (en) * | 2019-03-04 | 2019-05-17 | 中国科学院理化技术研究所 | A kind of liquid metal target and its method for preparing alloy film |
| CN110204764A (en) * | 2019-06-17 | 2019-09-06 | 中国科学院理化技术研究所 | A kind of drag reduction, heat-insulated polymeric pipe and the preparation method and application thereof |
| CN116022839A (en) * | 2021-10-26 | 2023-04-28 | 中国科学院理化技术研究所 | Preparation method for preparing micro-nano structure at one time, micro-nano structure and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050228097A1 (en) * | 2004-03-30 | 2005-10-13 | General Electric Company | Thermally conductive compositions and methods of making thereof |
| CN102802346A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院理化技术研究所 | Liquid-metal printed circuit board and preparation method thereof |
| US8679621B2 (en) * | 2010-06-18 | 2014-03-25 | Board Of Trustees Of The University Of Illinois | Materials and methods for autonomous restoration of electrical conductivity |
| KR20140043553A (en) * | 2012-09-24 | 2014-04-10 | 포항공과대학교 산학협력단 | Method of forming nano-structure |
| CN103811615A (en) * | 2014-01-28 | 2014-05-21 | 西安理工大学 | Preparation method of ZnO (Zinc Oxide) film for Schottky ZnO based LED (Light Emitting Diode) |
| CN103837913A (en) * | 2012-11-26 | 2014-06-04 | 中国科学院理化技术研究所 | Reflector and production process thereof |
-
2016
- 2016-06-24 CN CN201610472145.0A patent/CN107557718B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050228097A1 (en) * | 2004-03-30 | 2005-10-13 | General Electric Company | Thermally conductive compositions and methods of making thereof |
| US8679621B2 (en) * | 2010-06-18 | 2014-03-25 | Board Of Trustees Of The University Of Illinois | Materials and methods for autonomous restoration of electrical conductivity |
| CN102802346A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院理化技术研究所 | Liquid-metal printed circuit board and preparation method thereof |
| KR20140043553A (en) * | 2012-09-24 | 2014-04-10 | 포항공과대학교 산학협력단 | Method of forming nano-structure |
| CN103837913A (en) * | 2012-11-26 | 2014-06-04 | 中国科学院理化技术研究所 | Reflector and production process thereof |
| CN103811615A (en) * | 2014-01-28 | 2014-05-21 | 西安理工大学 | Preparation method of ZnO (Zinc Oxide) film for Schottky ZnO based LED (Light Emitting Diode) |
Non-Patent Citations (1)
| Title |
|---|
| DOUDRICK, K ET AL.: "Different Shades of Oxide: From Nanoscale Wetting Mechanisms to Contact Printing of Gallium-Based Liquid Metals", 《LANGMUIR》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108220924A (en) * | 2018-01-26 | 2018-06-29 | 中国科学院理化技术研究所 | A kind of preparation method of Copper thin film |
| CN108457079A (en) * | 2018-04-27 | 2018-08-28 | 中国科学院理化技术研究所 | A kind of liquid metal/carbon fibre composite and its preparation method and application |
| CN108457079B (en) * | 2018-04-27 | 2021-04-02 | 中国科学院理化技术研究所 | Liquid metal/carbon fiber composite material and preparation method and application thereof |
| CN109763109A (en) * | 2019-03-04 | 2019-05-17 | 中国科学院理化技术研究所 | A kind of liquid metal target and its method for preparing alloy film |
| CN110204764A (en) * | 2019-06-17 | 2019-09-06 | 中国科学院理化技术研究所 | A kind of drag reduction, heat-insulated polymeric pipe and the preparation method and application thereof |
| CN110204764B (en) * | 2019-06-17 | 2022-04-22 | 中国科学院理化技术研究所 | Drag-reduction and heat-insulation polymer pipeline and preparation method and application thereof |
| CN116022839A (en) * | 2021-10-26 | 2023-04-28 | 中国科学院理化技术研究所 | Preparation method for preparing micro-nano structure at one time, micro-nano structure and application thereof |
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