CN109910418A - Thermally conductive polytetrafluoroethylene film with porous structure and preparation method thereof - Google Patents

Thermally conductive polytetrafluoroethylene film with porous structure and preparation method thereof Download PDF

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CN109910418A
CN109910418A CN201910223864.2A CN201910223864A CN109910418A CN 109910418 A CN109910418 A CN 109910418A CN 201910223864 A CN201910223864 A CN 201910223864A CN 109910418 A CN109910418 A CN 109910418A
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polytetrafluoroethylene film
graphene
thermally conductive
preparation
porous structure
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CN109910418B (en
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陈军
王霄
倪海鹰
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Sichuan University
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Sichuan University
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Abstract

The preparation method of thermally conductive polytetrafluoroethylene film with porous structure, belongs to field of functional materials, comprising the following steps: 1: being bonded by hot pressing and fits to polypropylene non-woven fabric on polytetrafluoroethylene film;2: polytetrafluoroethylene film is handled using oxygen plasma;3: polytetrafluoroethylene film is dipped into dehydrated alcohol;4: preparing graphene soak;5: polytetrafluoroethylene film is dipped into graphene dispersing solution;6: soaked polytetrafluoroethylene film is taken out into drying.The present invention is the novel smooth thin evaporated film material of thin, tough, foldable, good toughness by the polytetrafluoroethylene film of graphene modified, and preparation method is simple, easy to operate, at low cost, is suitble to large-scale commercial production.

Description

Thermally conductive polytetrafluoroethylene film with porous structure and preparation method thereof
Technical field
The invention belongs to field of compound material, and in particular to a kind of thermally conductive polytetrafluoroethylene film with porous structure and Preparation method.
Background technique
Shortage of fresh water has become one of the global challenges of current most serious, and therefore, how efficiently to produce fresh water becomes Urgent problem to be solved, and be considered as a kind of economic measures for solving the problems, such as this using solar energy production fresh water.It is abundant Solar energy, which makes solar energy desalinize seawater, becomes one of most promising technology with wastewater treatment, while being also the hot spot of research.And The problem of traditional solar purified water resource handler is not able to solve dirt, other crucial disadvantages include needing to add The water of hot whole volume, the pollutant of periodic cleaning accumulation, and tact area needed for collecting enough sunlight.In recent years Come, realizes the efficient sun using floating structure and evaporate, do not need to occupy a large amount of soil, and can be directly on the water surface Arrangement.In order to reach high evaporation rate, the generation of heat is navigated to water-air interface by these structures, entire big to avoid heating The water (such as ocean) of volume.But complicated manufacture is generally required with the solar steam device that efficient steam generates Technique and high material cost, which has limited the extensive uses of these new technologies.Cost-effective solution is found to big Scale water process is of great significance.The development of the interface vapo(u)rization system of Driven by Solar Energy is mainly around solar absorber exhibition It opens, currently, researched and developed two class solar absorptive materials, i.e., carbon-based and plasma absorption body.
Due to the energy level of atomic nucleus pi-electron tight spacing in carbon-based material, there is them in entire solar spectrum extensively General absorption, excited electron relax towards the characteristics of ground state can discharge heat.Carbon-based material includes carbon black, CNT, graphene, GO, rGO Deng, due to its extensive light absorption, high stability is light-weight and inexpensive and have broad application prospects, be most name Optothermal material.Carbon-based material is free of toxic metals, has better stability than plasma in the sun, and can be easy Ground is made with solar heat using required macroscopic view, microcosmic and nanoscale form various structures.In view of cost, availability, Stability and toxicity, carbon-based optothermal material are very advantageously to select, and have been obtained in solar energy is evaporated and distilled and applies than it He widely explores material.
Preparing porous structure is the available strategy for improving many carbon material light absorptions, and wherein graphene and rGO have been obtained extensively General exploration.In addition, carbon material has very high thermal coefficient, this advantageously reduces the conductive heat loss of water.
Graphene is natural black material, be suitable for the broadband sun absorb, while also have absorptivity it is high, it is at low cost, The advantages that processing performance is good is up-and-coming absorber, so that graphene has high application in terms of solar energy evaporation Value.
Document " Wang Yonghu etc., graphene oxide-polytetrafluorethylenano nano composite material and performance " is elaborated PTFE powder Material is immersed in using in the modified graphene oxide of Silane coupling agent KH550 (kOG) dispersion liquid, after being dispersed with stirring, by solid Drying, compression molding, sintering, cutting, which are polished, is made composite material, but this method uses powder first, and needs oxygen Graphite alkene is modified, and finished product obtained is also required to just obtain final finished, the use of final products by complex process Effect is bad, and complex process, is unfavorable for industrialized production.
Summary of the invention
It is described the purpose of the present invention is to provide the thermally conductive polytetrafluoroethylene film and preparation method thereof with porous structure Method preparation process is simple, short preparation period, at low cost and suitable large-scale production;What is be prepared has porous evaporation structure Thermally conductive PTFE film material, floating Steaming structure can move together with water termination, can continuous work, it is high-efficient.
The technical solution adopted by the present invention is that:
The preparation method of thermally conductive polytetrafluoroethylene film with porous structure, comprising the following steps:
Step 1: being bonded by hot pressing and fit to polypropylene non-woven fabric on polytetrafluoroethylene film;
Step 2: using the polytetrafluoroethylene film for being bonded polypropylene non-woven fabric in oxygen plasma processing step 1;
Step 3: the polytetrafluoroethylene film after plasma treatment is dipped into dehydrated alcohol;
Step 4: graphene dispersing solution being added in distilled water, is stirred, and is ultrasonically treated 5~60min, is prepared into stone Black alkene soak;
Step 5: the polytetrafluoroethylene film that dehydrated alcohol is soaked is dipped into the graphene dispersing solution prepared, when immersion Between be 10~120min;
Step 6: soaked polytetrafluoroethylene film being taken out, using vacuum drying or heated-air drying or the direct side dried Formula is dried.
Further, in step 2, the time that oxygen plasma handles polytetrafluoroethylene film is 5-300s.
Further, in step 3, soaking time of the polytetrafluoroethylene film in dehydrated alcohol is 10~240min.
Further, the concentration for the graphene soak that prepared by step 4 is 0.1~1wt%, the diameter of graphene is 10~ 100nm.In order to reduce the loss of reflected light, optothermal material is normally manufactured as the nanostructure of high porosity, so that light exists Pore interior generates multiple reflections, the final absorption for increasing light.In the present invention, if the concentration of graphene soak is excessive, Then one layer of fine and close graphene can be will form in film surface, block the gap between polytetrafluoroethylene fibre;And concentration it is too low when, lead It causes the light absorption of graphene to reduce, is reduced so as to cause the heat of absorption, influence thermally conductive and evaporation efficiency, thus, by repeatedly Experiment, it is determined that above-mentioned concentration range.In addition, for the diameter of graphene, if more than the diameter in polytetrafluoroethylene fibre gap (220nm), then graphene can be only present in ptfe surface, then the content of graphene will drop in the composite Low, the absorption of sunlight and heat can also be reduced, and finally influence thermally conductive and evaporation efficiency;If being much smaller than the numerical value, such as low In 10nm, graphene can be easily gathered in the gap of polytetrafluoroethylene fibre, to block the gap of polytetrafluoroethylene (PTFE).
Further, the graphene of step 4 can also select graphene oxide, redox graphene or graphene microballoon.
Further, the drying temperature in step 6 is 50~150 DEG C.
Further, the structure of the thermally conductive PTFE film material with porous evaporation structure is that upper surface is hydrophobic, Lower surface is hydrophilic, and hydrophobic is the polytetrafluoroethylene film for covering one layer of graphene on one side, and hydrophilic is polypropylene non-woven fabric on one side (being made of polypropylene fibre, after it passes through plasma treatment, become 57 ° with the contact angle of water, that is, show as hydrophily)
The beneficial effects of the present invention are:
The thermally conductive PTFE film material with porous evaporation structure being prepared using the method is floated and is steamed Hair structure can be moved together with water termination, can the work of continuous high-efficient rate, porous evaporation structure is with wicking ability to heating zone It supplies water, the porous microstructure of small-bore and is exaggerated the effect that capillary supplies water to heating zone;There is graphene excellent light to inhale Yield and photothermal conversion;The polytetrafluoroethylene film being prepared simultaneously has different wetabilitys in upper and lower surface, hydrophilic Bottom surface can sufficiently be soaked by water, increased capillary pumpability, vaporized liquid sustainedly and stably with high-speed, hydrophobic table Face has self-cleaning ability, facilitates polytetrafluoroethylene film and swim in water surface.It is prepared with porous evaporation structure Thermally conductive PTFE film material can be realized efficient sewage purification, the cleaning of the water such as sea water desalination.
In addition, according to polytetrafluoroethylene film gap feature, by optimizing the concentration and diameter of graphene, so that the two reaches Best match, and then the advantages of reach high efficiency extinction.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the thermally conductive PTFE film material that the present invention has porous evaporation structure, 1, cover The polytetrafluoroethylene film of one layer of graphene of lid, 2, polypropylene non-woven fabric fibrous layer;
Fig. 2 be embodiment 1 prepare thin-film material scanning electron microscope diagram, 10 μm of (a), (b) 1 μm;
Fig. 3 is solar energy water evaporation rate curve graph of the thin-film material of the preparation of embodiment 1 under 1KW intensity;
Fig. 4 is solar energy water evaporation rate curve graph of the thin-film material of the preparation of embodiment 2 under 1KW intensity;
Fig. 5 is solar energy water evaporation rate curve graph of the thin-film material of the preparation of embodiment 3 under 1KW intensity;
Fig. 6 is solar energy water evaporation rate curve graph of the thin-film material of the preparation of embodiment 4 under 1KW intensity;
Fig. 7 is solar energy water evaporation rate curve graph of the thin-film material of the preparation of embodiment 5 under 1KW intensity.
Specific embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
The preparation method of thermally conductive PTFE film material with porous structure, comprising the following steps:
Step 1: being bonded by hot pressing and fit to polypropylene non-woven fabric on polytetrafluoroethylene film;
Step 2: using the polytetrafluoroethylene film for being bonded polypropylene non-woven fabric in oxygen plasma processing step 1, processing Time 300s;
Step 3: the polytetrafluoroethylene film after plasma treatment is impregnated into 240min in dehydrated alcohol;
Step 4: graphene dispersing solution being added in distilled water, is stirred, and be ultrasonically treated 60min, is prepared into concentration For 0.4% graphene soak, the diameter of graphene is 10-100nm;
Step 5: the polytetrafluoroethylene film that dehydrated alcohol is soaked is dipped into the graphene dispersing solution prepared, when immersion Between be 30min;
Step 6: soaked polytetrafluoroethylene film being taken out, finished product is dried in vacuo to obtain at 100 DEG C.
Embodiment 2
The preparation method of thermally conductive PTFE film material with porous structure, comprising the following steps:
Step 1: being bonded by hot pressing and fit to polypropylene non-woven fabric on polytetrafluoroethylene film;
Step 2: using the polytetrafluoroethylene film for being bonded polypropylene non-woven fabric in oxygen plasma processing step 1, processing Time 300s;
Step 3: the polytetrafluoroethylene film after plasma treatment is impregnated into 120min in dehydrated alcohol;
Step 4: graphene dispersing solution being added in distilled water, is stirred, and be ultrasonically treated 30min, is prepared into concentration For 0.6% graphene soak, the diameter of graphene is 10-100nm;
Step 5: the polytetrafluoroethylene film that dehydrated alcohol is soaked is dipped into the graphene dispersing solution prepared, when immersion Between be 10min;
Step 6: soaked polytetrafluoroethylene film being taken out, is directly dried at 100 DEG C.
Embodiment 3
The preparation method of thermally conductive PTFE film material with porous structure, comprising the following steps:
Step 1: being bonded by hot pressing and fit to polypropylene non-woven fabric on polytetrafluoroethylene film;
Step 2: using the polytetrafluoroethylene film for being bonded polypropylene non-woven fabric in oxygen plasma processing step 1, processing Time 300s;
Step 3: the polytetrafluoroethylene film after plasma treatment is impregnated into 100min in dehydrated alcohol;
Step 4: graphene dispersing solution being added in distilled water, is stirred, and be ultrasonically treated 30min, is prepared into concentration For 0.1% graphene soak, the diameter of graphene is 10-100nm;
Step 5: the polytetrafluoroethylene film that dehydrated alcohol is soaked is dipped into the graphene dispersing solution prepared, when immersion Between be 60min;
Step 6: soaked polytetrafluoroethylene film being taken out, is directly dried at 150 DEG C.
Embodiment 4
The preparation method of thermally conductive PTFE film material with porous structure, comprising the following steps:
Step 1: being bonded by hot pressing and fit to polypropylene non-woven fabric on polytetrafluoroethylene film;
Step 2: using the polytetrafluoroethylene film for being bonded polypropylene non-woven fabric in oxygen plasma processing step 1, processing Time 200s;
Step 3: the polytetrafluoroethylene film after plasma treatment is impregnated into 50min in dehydrated alcohol;
Step 4: graphene dispersing solution being added in distilled water, is stirred, and be ultrasonically treated 10min, is prepared into concentration For 1% graphene soak, the diameter of graphene is 10-100nm;
Step 5: the polytetrafluoroethylene film that dehydrated alcohol is soaked is dipped into the graphene dispersing solution prepared, when immersion Between be 90min;
Step 6: soaked polytetrafluoroethylene film being taken out, is directly dried at 150 DEG C.
Embodiment 5
The preparation method of thermally conductive PTFE film material with porous structure, comprising the following steps:
Step 1: being bonded by hot pressing and fit to polypropylene non-woven fabric on polytetrafluoroethylene film;
Step 2: using the polytetrafluoroethylene film for being bonded polypropylene non-woven fabric in oxygen plasma processing step 1, processing Time 200s;
Step 3: the polytetrafluoroethylene film after plasma treatment is impregnated into 50min in dehydrated alcohol;
Step 4: graphene dispersing solution being added in distilled water, is stirred, and be ultrasonically treated 10min, is prepared into concentration For 1% graphene soak, the diameter of graphene is 10-100nm;
Step 5: the polytetrafluoroethylene film that dehydrated alcohol is soaked is dipped into the graphene dispersing solution prepared, when immersion Between be 120min;
Step 6: soaked polytetrafluoroethylene film being taken out, is directly dried at 150 DEG C.
Wherein, soaking time mainly will affect graphene in the attachment uniformity of PolytetrafluoroethylFilm Film and attachment The quality of power, to influence evaporation effect.
The thermally conductive PTFE film material (as shown in Figure 1) with porous evaporation structure that embodiment 1 is obtained into Row Surface Characterization encloses graphene from the scanning electron microscope diagram thin-film material surface (as shown in Figure 2) that can be seen that, and thin Graphene is equally filled in the gap of film, illustrates that graphene is successfully attached in ptfe surface and fibre gap.
To Examples 1 to 5 preparation the thermally conductive PTFE film material with porous evaporation structure intensity be 1kw Solar energy under carry out solar energy water steam generation test, test case is to fill water to beaker, on beaker cover the present invention The thin-film material of each embodiment, comparative example are that beaker fills water, but what is covered is no athermanous polytetrafluoro of porous evaporation structure Vinyl film material, is as a result shown in Fig. 3~7.
It was found that under 1kw intensity, the beaker of the thermally conductive PTFE film material equipped with porous evaporation structure, the sun Energy thermal evaporation effect is obvious, this is because the polytetrafluoroethylene film being prepared has different wetabilitys in upper and lower surface, Hydrophilic bottom surface can sufficiently be soaked by water, increased capillary pumpability, vaporized liquid sustainedly and stably with high-speed, hydrophobic Surface, there is self-cleaning ability, facilitate polytetrafluoroethylene film and swim in water surface, while graphene has excellent light Absorptivity and photothermal conversion.

Claims (8)

1. the preparation method of the thermally conductive polytetrafluoroethylene film with porous structure, which comprises the following steps:
Step 1: being bonded by hot pressing and fit to polypropylene non-woven fabric on polytetrafluoroethylene film;
Step 2: using the polytetrafluoroethylene film for being bonded polypropylene non-woven fabric in oxygen plasma processing step 1;
Step 3: the polytetrafluoroethylene film after plasma treatment is dipped into dehydrated alcohol;
Step 4: graphene dispersing solution being added in distilled water, is stirred, and is ultrasonically treated 5~60min, is prepared into graphene Soak;
Step 5: the polytetrafluoroethylene film that dehydrated alcohol is soaked is dipped into the graphene dispersing solution prepared, and soaking time is 10~120min;
Step 6: soaked polytetrafluoroethylene film is taken out, using vacuum drying heated-air drying or directly dry by the way of into Row drying.
2. the preparation method of the thermally conductive polytetrafluoroethylene film with porous structure as described in claim 1, which is characterized in that In step 2, the time that oxygen plasma handles polytetrafluoroethylene film is 5-300s.
3. the preparation method of the thermally conductive polytetrafluoroethylene film with porous structure as described in claim 1, which is characterized in that In step 3, soaking time of the polytetrafluoroethylene film in dehydrated alcohol is 10~240min.
4. the preparation method of the thermally conductive polytetrafluoroethylene film with porous structure as described in claim 1, which is characterized in that The concentration of graphene soak prepared by step 4 is 0.1~1wt%, and the diameter of graphene is 10~100nm.
5. the preparation method of the thermally conductive polytetrafluoroethylene film with porous structure as described in claim 1, which is characterized in that The graphene of step 4 can also select graphene oxide, redox graphene or graphene microballoon.
6. the preparation method of the thermally conductive polytetrafluoroethylene film with porous structure as described in claim 1, which is characterized in that Drying temperature in step 6 is 50~150 DEG C.
7. special using the thermally conductive polytetrafluoroethylene film with porous structure of any the method preparation of claim 1~6 Sign is that the structure of the film is that upper surface is hydrophobic, and lower surface is hydrophilic, and hydrophobic is the polytetrafluoro for covering one layer of graphene on one side Vinyl film, hydrophilic is the polypropylene non-woven fabric that water contact angle is 57 ° on one side.
8. the application of the thermally conductive polytetrafluoroethylene film with porous structure as claimed in claim 7, which is characterized in that be used for In sewage purification or field of seawater desalination.
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EP0398508A1 (en) * 1989-04-20 1990-11-22 Japan Gore-Tex, Inc. A separation membrane for use in a pervaporation process and a separation method thereof
CN101462024A (en) * 2008-12-24 2009-06-24 北京时代沃顿科技有限公司 Composite reverse osmosis membrane with high-intensity anti-pollution layer and preparation method thereof
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