CN1508003A - Method for preparing plymer ocmposite nano particle molecular membrane - Google Patents
Method for preparing plymer ocmposite nano particle molecular membrane Download PDFInfo
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- CN1508003A CN1508003A CNA02155692XA CN02155692A CN1508003A CN 1508003 A CN1508003 A CN 1508003A CN A02155692X A CNA02155692X A CN A02155692XA CN 02155692 A CN02155692 A CN 02155692A CN 1508003 A CN1508003 A CN 1508003A
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Abstract
The present invention relates to a preparation method of polymer composite nano particle molecular film. Said method adopts molecular deposition technique, and includes the following steps: immersing the substrate in the mixed solution of H2SO4 and H2O2, taking out and cleaning, then immersing said substrate in polyacrylamide solution, taking out and cleaning, then immersing said substrate in polymer solution, and repeating the steps of immersing in polyacrylamide solution and immersing in polymer solution so as to obtain the required number of film layers or heating the substrate impregnated with polymer under the protection of nitrogen gas. Said substrate can be quartz substrate, glass substrate or silicon wafer substrate, and the polymer solution can be graphite oxide solution or polyacrylic acid covered titanium dioxide nano particles solution.
Description
Technical field
The invention discloses a kind of preparation method of composite nano-polymers particle molecular film, belong to field of material engineering technology.
Background technology
Wearing and tearing are the key factors that influence Micro Electro Mechanical System and magnetic-memory system operation steady in a long-term, and developing a kind of can practical film be the important channel that addresses this problem.At present, industry to the solution of this problem mainly concentrate on to molecule self-assembled film, LB (Langmuir---Blodgett) in the compound research of film and these two kinds of films, and the wearability of these two kinds of films is poor, has very important Practical significance so develop a kind of molecular film with good abrasion resistance.
Since the nineties, had the people to prepare multiple composite membrane with the method for molecule deposition, also once be used for the research of tribology aspect, use but limited it owing to wearability is relatively poor, reason is that the bond strength in the film is little.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of composite nano-polymers particle molecular film, to reach the frictional dissipation problem that solves Micro Electro Mechanical System and magnetic-memory system.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of composite nano-polymers particle molecular film, this method adopts molecular deposition technique, and this method comprises the steps: at least
Step 1: substrate is immersed H
2SO
4With H
2O
2Mixed solution in, take out afterwash;
Step 2: the substrate after will cleaning immerses in the polypropylene amine solution, takes out afterwash;
Step 3: the substrate after cleaning in the above-mentioned steps 2 is immersed in the polymer solution, take out afterwash;
Step 4: repetition above-mentioned steps 2,3 reaches the needed film number of plies or the substrate after cleaning in the above-mentioned steps 3 is heated.
Described heating steps comprises:
At first: the substrate after cleaning in the step 3 is dried up with nitrogen;
Then: the substrate after above-mentioned the drying up was heated 2 hours under protection of nitrogen gas.
Described substrate is quartz substrate or glass substrate or silicon chip substrate.
Described polymer solution is graphite oxide solution or polyacrylic acid cladding titanium dioxide nano particle solution.
The preparation method of composite nano-polymers particle molecular film provided by the present invention utilizes the method for heating, changes the electrostatic attraction of polymer dielectric between multi-layer compound film the combining form of chemical bond into, and the reaction equation of its transition process is as follows:
A: be polyacrylic acid (PAA) composite nanoparticle or graphite oxide;
B: be polypropylene amine (PAH).
Utilize the laminated film of this method preparation to have good wearability, and have low friction, wear-resistant advantage.
Description of drawings
Fig. 1 is the structural representation of two kinds of polymer composite films of polypropylene amine/graphite oxide provided by the present invention;
Fig. 2 is the structural representation of polypropylene amine provided by the present invention/poly-propionic acid cladding titanium dioxide nano particle laminated film;
Fig. 3 is the structural representation of polypropylene amine/graphite oxide provided by the present invention/polypropylene amine/polyacrylic acid cladding titanium dioxide nano particle laminated film;
The specific embodiment
Composite nano-polymers particle molecular film provided by the present invention can be the single polymers laminated film, also can be the multiple polymers laminated film.
Below, in conjunction with specific embodiments, the present invention is described in further detail.
Before preparation molecular film provided by the present invention, should at first prepare the polymer solution that is used for molecule deposition.In the following embodiment that provides, the polymer solution of employing is that graphite oxide solution, polyacrylic acid (PAA) coat TiO
2Nano-particle solution.The preparation method of these two kinds of solution is as follows:
1, the preparation of graphite oxide solution
Get graphite powder 5g, add 15g KClO
3With 35ml HNO
3In be heated to 60-90 ℃ after evenly, keep and stirred 24 hours, filter then, graphite powder after the oxidation is washed with 0.1M HCl, it is neutral washing to pH value with 0.1M NaCl then, at last graphite powder is washed with water and remove NaCl, again it is dissolved in the water and regulates PH=4-7, promptly obtain to be used to prepare the graphite oxide solution of film.
2, polyacrylic acid (PAA) coats TiO
2The preparation of nano-particle solution
The PAA aqueous solution 100mml that gets 0.1M is heated to 60 ℃, and the ethanolic solution 20ml with 0.01M metatitanic acid four own fat dropwise adds in the above-mentioned solution then, keeps and stirs 3 hours, aging 24 hours of colloidal sol.At last the colloidal sol centrifugation is promptly obtained being used to prepare the PAA (TiO of film
2) nano-particle solution.
Embodiment one
The preparation method of two kinds of polymer composite films of polypropylene amine/graphite oxide:
The quartz substrate that present embodiment is used immerses 80 ℃ H
2SO
4: H
2O
2In=75: 25 the solution 30 minutes, take out the abundant washes clean of back water, quartz substrate after will cleaning then immerses in poly-propylamine (PAH) solution, taking out the back cleans, immerse above-mentioned the preparation in the graphite oxide solution of finishing again, clean once more after the taking-up, immerse again in the PAH solution, obtain the laminated film that the quartz substrate surface has three one polymer layer.Behind three layers of composite membrane that reach above-mentioned requirements; this quartz substrate taking-up is dried up with nitrogen; and under protection of nitrogen gas, heated 2 hours, make the electrostatic attraction of laminated film interlayer change chemical bonded refractory into joint efforts, finish the preparation of two kinds of polymer composite films of polypropylene amine/graphite oxide.
The deck structure of this polymer composite film comprises quartz substrate 1, bottom polypropylene amine thin layer 2, graphite oxide thin layer 3 and polypropylene amine top layer 4 as shown in Figure 1 among the figure; Each interlayer adhesion is the chemical bond combination.
Embodiment two
The preparation method of polypropylene amine/polyacrylic acid cladding titanium dioxide nano particle laminated film:
After according to embodiment one described method the quartz substrate preliminary treatment being finished, the quartz substrate after cleaning is immersed in polypropylene amine (PAH) solution, take out the back and clean.Immerse above-mentioned the preparation in the polyacrylic acid cladding titanium dioxide nano particle solution of finishing again, clean once more after the taking-up, immerse again in the PAH solution, obtain the laminated film that the quartz substrate surface has three one polymer layer of polypropylene amine/polyacrylic acid cladding titanium dioxide nano particle thus.Follow-up dries up, protects heating means identical with embodiment one, so do not give unnecessary details.
The deck structure of polypropylene amine/polyacrylic acid cladding titanium dioxide nano particle laminated film as shown in Figure 2, comprise quartz substrate 1, bottom polypropylene amine thin layer 2, polyacrylic acid cladding titanium dioxide nano particle thin layer 5 and polypropylene amine top layer 4 among the figure, each interlayer adhesion is the chemical bond combination.
According to disclosed technical scheme of above-mentioned two embodiment and method of operating, can also make multiple, multi-layer compound film as required, for example: polypropylene amine/graphite oxide/polypropylene amine/polyacrylic acid cladding titanium dioxide nano particle laminated film, as shown in Figure 3.Among the figure, this film comprises quartz substrate 1, bottom polypropylene amine thin layer 2, graphite oxide thin layer 3, polypropylene amine intermediate layer 6, polyacrylic acid cladding titanium dioxide nano particle thin layer 5, and each interlayer adhesion is the chemical bond combination.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (10)
1, a kind of preparation method of composite nano-polymers particle molecular film, this method adopts molecular deposition technique, and it is characterized in that: this method comprises the steps: at least
Step 1: substrate is immersed H
2SO
4With H
2O
2Mixed solution in, take out afterwash;
Step 2: the substrate after will cleaning immerses in the polypropylene amine solution, takes out afterwash;
Step 3: the substrate after cleaning in the above-mentioned steps 2 is immersed in the polymer solution, take out afterwash;
Step 4: repetition above-mentioned steps 2,3 reaches the needed film number of plies or the substrate after cleaning in the above-mentioned steps 3 is heated.
2, the preparation method of composite nano-polymers particle molecular film according to claim 1 is characterized in that: described preparation process 1 is specially: substrate is immersed 60-90 ℃, and volume ratio is 75: 25 H
2SO
4With H
2O
2Mixed solution in 30 minutes, take out the back and clean described H with deionized water
2SO
4Concentration is 98%, H
2O
2Concentration is 30%.
3, the preparation method of composite nano-polymers particle molecular film according to claim 1 is characterized in that: described preparation process 2 is specially: substrate after will cleaning immersed in the polypropylene amine solution of 0.001M 30 minutes, took out afterwash.
4, the preparation method of composite nano-polymers particle molecular film according to claim 1, it is characterized in that: described preparation process 3 is specially: the substrate after cleaning in the above-mentioned steps 2 was immersed in the polymer solution 6 hours, take out the back and clean with deionized water.
5, according to the preparation method of claim 1 or 3 or 4 described composite nano-polymers particle molecular films, it is characterized in that: described preparation process 4 is specially: repetition above-mentioned steps 2,3 reaches the needed film number of plies or the substrate after cleaning in the above-mentioned steps 3 is heated under protection of nitrogen gas.
6, the preparation method of composite nano-polymers particle molecular film according to claim 1 or 5, it is characterized in that: described heating steps comprises:
At first: the substrate after cleaning in the step 3 is dried up with nitrogen;
Then: the substrate after above-mentioned the drying up was heated 2 hours under protection of nitrogen gas.
7, according to the preparation method of claim 1 or 2 or 3 or 4 described composite nano-polymers particle molecular films, it is characterized in that: described substrate is quartz substrate or glass substrate or silicon chip substrate.
8, according to the preparation method of claim 1 or 4 described composite nano-polymers particle molecular films, it is characterized in that: described polymer solution is graphite oxide solution or polyacrylic acid cladding titanium dioxide nano particle solution.
9, according to the preparation method of claim 1 or 4 or 10 described composite nano-polymers particle molecular films, it is characterized in that: the preparation of described graphite oxide solution is finished by following steps:
In graphite powder, add solid K ClO
3With dense HNO
3Solution, stirring is heated to 60-90 ℃ and carries out oxidation reaction, keeps and stirs 24 hours, filters then;
After using the HCL solution washing graphite powder of 0.1M again, extremely neutral with the NaCl solution washing of 0.1M;
Wash graphite powder at last with water, remove NaCl, being scattered in graphite powder in the water and regulating the pH value is 4-7.
10, according to the preparation method of claim 1 or 4 or 10 described composite nano-polymers particle molecular films, it is characterized in that: the preparation of described polyacrylic acid cladding titanium dioxide nano particle solution is finished by following steps:
The polyacrylic acid aqueous solution with 0.1M is heated to 60 ℃ earlier;
Ethanolic solution with 0.01M metatitanic acid four own fat dropwise adds in the above-mentioned polyacrylic acid aqueous solution again, keeps and stirs 3 hours, aging 24 hours of colloidal sol;
With the colloidal sol centrifugation, obtain polyacrylic acid cladding titanium dioxide nano particle solution at last.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155692 CN1270883C (en) | 2002-12-13 | 2002-12-13 | Method for preparing plymer ocmposite nano particle molecular membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155692 CN1270883C (en) | 2002-12-13 | 2002-12-13 | Method for preparing plymer ocmposite nano particle molecular membrane |
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|---|---|
| CN1508003A true CN1508003A (en) | 2004-06-30 |
| CN1270883C CN1270883C (en) | 2006-08-23 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331922C (en) * | 2005-11-01 | 2007-08-15 | 浙江大学 | Covalent layer-by-layer self-assembling process for constructing polymer film on planar substrate |
| CN101538370B (en) * | 2008-03-20 | 2011-07-27 | 中国石油大学(北京) | Polymeric composite in-situ growth nano-particle molecular film and preparation method thereof |
| CN101602279B (en) * | 2009-07-15 | 2012-07-25 | 中国石油大学(北京) | In-site silver nano-particle/polymer composite molecular film and preparation method thereof |
| CN102658068A (en) * | 2012-05-03 | 2012-09-12 | 天津大学 | Polyacrylamide-titanium oxide hybrid porous microcapsules and preparation method |
| CN111072083A (en) * | 2018-10-18 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Seawater evaporation desalination membrane material, preparation method and application thereof |
-
2002
- 2002-12-13 CN CN 02155692 patent/CN1270883C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331922C (en) * | 2005-11-01 | 2007-08-15 | 浙江大学 | Covalent layer-by-layer self-assembling process for constructing polymer film on planar substrate |
| CN101538370B (en) * | 2008-03-20 | 2011-07-27 | 中国石油大学(北京) | Polymeric composite in-situ growth nano-particle molecular film and preparation method thereof |
| CN101602279B (en) * | 2009-07-15 | 2012-07-25 | 中国石油大学(北京) | In-site silver nano-particle/polymer composite molecular film and preparation method thereof |
| CN102658068A (en) * | 2012-05-03 | 2012-09-12 | 天津大学 | Polyacrylamide-titanium oxide hybrid porous microcapsules and preparation method |
| CN111072083A (en) * | 2018-10-18 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Seawater evaporation desalination membrane material, preparation method and application thereof |
| CN111072083B (en) * | 2018-10-18 | 2022-05-31 | 中国科学院宁波材料技术与工程研究所 | Seawater evaporation desalination membrane material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1270883C (en) | 2006-08-23 |
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