CN1748877A - Process for preparing functional heat transfer surface - Google Patents
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- CN1748877A CN1748877A CNA2005100473519A CN200510047351A CN1748877A CN 1748877 A CN1748877 A CN 1748877A CN A2005100473519 A CNA2005100473519 A CN A2005100473519A CN 200510047351 A CN200510047351 A CN 200510047351A CN 1748877 A CN1748877 A CN 1748877A
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Abstract
The present invention relates to heat transfer and energy saving technology, and is especially technology of modifying metal surface with functional coating and applying the modified metal surface in heat exchanger. The present invention features that paint is coated in the surface of heat exchanger and high temperature heat treated to resist corrosion, resist scale and raise heat efficiency. The coating contains fluoro resin in 60-70 wt%, adhesion promoting resin 20-25 wt%, heat conducting stuffing 5-10 wt%, and nanometer particle 0.5-3 wt%, and has thickness of 5-15 micron and thermal conductivity of 0.3-1.5 W/m.K. The coating makes condensed water in the heat exchange surface form drops with high heat conductance, and results in high anticorrosion and long service life of the coated heat exchanger.
Description
Technical field
The invention belongs to augmentation of heat transfer and field of energy-saving technology, relate to functional heat transfer surface material and preparation method thereof.Be particularly related to function of use coating modification carried out in the metal surface, with the modified metal surface applications in heat transmission equipment.
Background technology
Steam condensation heat transfer process has broad application background in fields such as chemical industry, refrigeration, generating, power and spacecraft heat control techniques, condensate liquid is the key factor that influences condensation heat transfer efficient in the cohesion form of heating surface, the heat transfer coefficient of dropwise condensation will be higher than the heat transfer coefficient of film condensation far away, but industrial condensing surface commonly used mostly is metal material, be easy wetting surface, so mostly be film condensation in the practical application.In principle, the approach of enforcing condensation heat transfer has two: increase heat transfer area and utilize surface tension etc. to be used for the attenuate condensate film, conventional method majority is the surface tension element that once proposed condensing surface by the Webb that the geometry that changes condensing surface is realized, utilize the variation of the radius of curvature in fin cross section in the liquid film that flows along fin, to form barometric gradient, that quickens liquid flows the augmentation of heat transfer effect.Daniel etc. introduce the conceptual approach of surface tension gradient because the factors such as autohemagglutination of surface tension gradient and liquid self drive liquid motion or shop cloth, the surface of solids that special surface processing technique preparation has surface tension gradient, realize the Marangoni effect artificially, move to easily wetting direction thereby can drive surface of solids liquid, thus enforcing condensation heat transfer.No matter the effect of first this method augmentation of heat transfer is comparatively difficult with regard to processing, be difficult for original heat-transfer equipment is transformed.
Under the general industry condition, keep keep for a long time dropwise condensation than the difficulty, the bottleneck of problem is that the preparation technology of the special surface that dropwise condensation is required is also not really perfect.In addition, steam condensation form or can be described as transition or condensation by mixing state between membranaceous and drip between the shape completely under many situations, and the heating surface that the experiment report has a low surface free energy also is contributive for the reinforcement of this type of condensation heat transfer.The new approaches that proposition condensation forms such as hippology tiger are divided and condensation heat transfer is strengthened are that the condensation heat transfer characteristic is to increase along with the increase of surface free energy difference, correspondingly, condensation form also will begin from the film condensation of beginning, changes intact dropwise condensation at last into through dripping film coexistence channel kenel.Between two critical points, the surface free energy difference is significant too for augmentation of heat transfer to the influence of the flow behavior of condensate film.This selection for the enforcing condensation heat transfer surface of the lower organic vapor of surface free energy provides guiding foundation.By selecting suitable face coat to reach suitable condensation intensify heat transmission effect, understand the mechanism of surface characteristic enforcing condensation heat transfer, Development of New Generation surface strengthening technology from a kind of brand-new viewpoint.
Realize the main following several classes of surfacing of dropwise condensation: organic accelerator, metal and compound thereof, organic high molecular polymer and other low-surface-energy materials.
(1) having the organic compound of hydrophobic group, is that the method that dropwise condensation is commonly used is realized in the laboratory as chain aliphatic acid, mercaptan, montan waxes etc. such as oleic acid, stearic acid.The characteristics of this class material are to have dissymmetrical structure.When its molecule combined with the metal surface with physics or chemisorption, nonpolar hydrophobic group was towards vapour phase, thereby reduced the metallic surface energy.The adding method of this class material is by directly being coated on the condensing surface or utilizing so-called ' self-assembling ' to generate the monolayer promoting layer from the teeth outwards and add two kinds of steam continuously or with gap.Owing to have the weak point in service life, pollute problems such as condensate liquid and erode metallic surfaces, limited the use of this class material, generally only be used for realizing the research of dropwise condensation heat transfer mechanism in the laboratory.
(2) metal and compound thereof: this class material comprises the amorphous alloy of noble metal, chromium, metal sulfide and metals such as gold.Studies show that can form comparatively stable dropwise condensation on gold surface, the solubility of metal sulfide in water is extremely low, therefore can be used to realize the dropwise condensation of water vapour.It is nearly 10 that discoveries such as Erb can be kept the dropwise condensation of water vapour at the surface of low-carbon steel that scribbles silver sulfide, 000h, but experimental repeatability is bad.
(3) organic polymer coating: high molecular polymer (making fluorocarbons especially) has quite low surface can, decapacitation realizes outside the dropwise condensation of the working medium (as water) that surface tension is bigger that this type of material is an effective way of the very little organic working medium dropwise condensation of realization surface tension.Erb and Thelen have prepared Parylene and ptfe surface with the method for gas deposition, still keep good dropwise condensation, heat transfer coefficient to improve 1.5 times after the continued operation of 2400h.Marto etc. are coating tetrafluoroethylene on smooth and coarse matrix, and it is about 12 that dropwise condensation is kept on this surface, 000h, and condensation coefficient improves 5 times, and finds that the life-span of dropwise condensation is not only relevant with the thickness of coating, also relevant with the character of body.Employing ion beam dynamic mixing injection technologies such as hippology tiger prepare polytetrafluoroethylene film, and for copper base PTFE surface, heat flux improves 0.3～0.4 times, and overall heat-transfer coefficient improves 0.4～5.5 times, and condensation coefficient improves 1.6～28.6 times.Though these surfaces can form more stable dropwise condensation in the laboratory, because process for treating surface, extensive strengthening surface preparation waits some problems, and industrial applications is all failed to realize in these surfaces.
(4) other material: Koch etc. carry out condensation test with Leipertz with the surface of coating diamond-like film (DLC), and the result shows on the DLC surface can form stable dropwise condensation.When in DLC, adding F, Si, during elements such as Si/O, the contact angle that liquid forms drop from the teeth outwards is bigger, and condensation coefficient is also bigger.Because diamond-film-like itself has and is similar to adamantine character, as wearability, chemical inertness, anti acid alkali performance, high-termal conductivity and low-surface-energy etc., therefore, DLC provides a new way for augmentation of heat transfer, but since at present the DLC coating technique that is that all right is ripe, limited the application of DLC.
For surface modification, some are researched and analysed to promote the steam condensation heat transfer based on above, develop a kind of preparation simply, and cost is low, is suitable for large-scale industrial application, and the strengthening surface of function admirable is the work that helps the novelty of energy-saving and environmental protection.
Summary of the invention
The purpose of this invention is to provide a kind of functional coating modification is carried out in the metal surface, the modified metal surface applications in heat transmission equipment, is realized that heat exchange surface has anticorrosion, anti-tartar, and can reach the effect that improves heat exchange efficiency.The surface that can overcome the metal surface can be high, to shortcomings such as special condensation working medium corrosion-resistant, easy foulings.The heat exchange surface modification that can be used for materials such as carbon steel, copper alloy, aluminium alloy is used.
Technical scheme of the present invention is:
For achieving the above object, technical conceive of the present invention is by the low-surface-energy Organic fluoride carbon coating that adopts nano modification modification to be carried out in the condensing heat-exchange metal surface to handle.Face coat main component after the modification is the thermostable fluorine carbon coating; Enrichment nano particle on the metal surface can reduce the physical difference of coating and collective, has played the over effect of rerum natura between metal and the organic matter, improves the stability and the service life of coating; The metal of high thermal conductivity or the heat conductivility that nonmetal inorganic filler improves face coat have been added in the coating.
The used resin of the present invention is the thermoplastic fluoroelastomer carbon resin, as copolymer (FEP) of polytetrafluoroethylene (PTFE), Kynoar (PVDF), tetrafluoroethene-perfluoro alkoxy ether copolymer (PFA), tetrafluoroethene-hexafluoro-propylene etc., polymer-modified based on the tetrafluoroethene that contains the functional group, its content is 25～35%; In coating except that above-mentioned fluorocarbon resin and be equipped with all good multiple polar group high score subclass adhesive force of hear resistance and adhesive force and promote resin, as acrylic resin, epoxy resin, polyamide, polyamidoimide, polyurethane, polyphenylene sulfide equal size 10～15%; Solid packing is generally selected superfine cupper powder, aluminium powder, silver powder, graphite, carbon black and other inorganic oxides, nitride for use, as SiC, Si
3N
4, Al
2N
3, TiN, TiC, TiCN, Al
2O
3, the good sheet particulates 1～3% of thermal conductivity such as CrxNy, ZrN; The applying working condition bigger to temperature fluctuation, other adds nanometer 0.5～2%, as copper, aluminium, chromium, oxide or TiO
2, ZnO etc., with the hardness and the compactness of the tack, stability and the coating that improve coating and matrix; Solvent and an amount of levelling agent, viscosity are transferred knot agent and stabilizing agent etc., and content is 35～55%.Generate water-based or organic solvent decentralized high-temperature baking type coating can dividing, and carry out preparing nano modification high-temperature baking type heat exchange coating after mixed fully the dispersion with the water-based or the solvent-borne type dispersion liquid of nanometer by above-mentioned group.
Construction technology:
The fluorocarbon coating of the present invention's preparation can carry out one or many by method heat exchanging surfaces such as electrostatic spraying, aerial sprayings and apply.
To carry out strict preliminary treatment to matrix material before applying:
1. matrix surface is carried out degreasing, rust cleaning, sandblast or with the fine sandpaper alligatoring of polishing;
2. clean with acetone and dry up the back spraying, air compressor pressure is controlled at 0.3～0.6MPa, guarantees high atomisation.
3. will spray good base material and put into baking oven, temperature-gradient method heat treatment, heat treated temperature adopts segmentation to carry out, and coating is below 150 ℃, and programming rate is 3 ℃/min; In the time of 130～150 ℃ 1 ℃/min; In the time of 150～380 ℃ 5 ℃/min; 380～400 ℃ of insulation 30min; Slowly reduce to room temperature with 3 ℃/min speed.Kynoar (PVDF) heat-treat condition is different with other resin, and room temperature to 150 ℃ is 3 ℃/min, and insulation is 10 minutes in the time of 150 ℃, and 150～280 ℃ is 5 ℃/min, and insulation is 20 minutes in the time of 280 ℃, slowly reduces to room temperature with 3 ℃/min speed afterwards.Heat treatment process adopts nitrogen protection, avoids base material and coating oxidation when heat treatment.Because the melt viscosity of fluorocarbon resin is bigger, the plastic phase behind glass transition temperature will have time enough to make the abundant levelling of coating, makes any surface finish densification.
4. the coating of the present invention's preparation needs disposable thermal sintering.
Effect of the present invention and benefit are:
The present invention is used for the modification of heat exchanger surface and handles, because coating surface can hang down to be used in the steam condensing heat exchanger and can realize dropwise condensation, plays the synergy of augmentation of heat transfer, mass transfer and anticorrosion anti-tartar.The traditional relatively heat exchange surface of modified surface of the nano modification fluorocarbon coating preparation that the present invention selects for use has following advantage: the many excellent properties that demonstrated fully fluorocarbon polymer, as high temperature heat-resistant stability, excellent chemical resistance, self-cleaning performance etc. can be hanged down in the surface.The nontoxic nonpolluting coating of the present invention preparation is used the fouling corrosion effect that can alleviate heat exchange surface in easily fouling, corrosion in than serious environmental.
Because the compound use of nano-powder particle improves the ageing resistance of coating again, improved the rheological characteristic of coating, improve adhesive force of coatings, hardness of film, fineness etc.; Improved the thermal dilation difference with matrix, adhesive force is significantly improved.Improve the volume of filler in the coating and fill density, reduce pin hole and capillarity, improve the shielding action of coating corrosive medium.The purpose that adopts ultra-fine heat filling is to improve the heat conductivility of coating, reduces the additional thermal resistance of coating.
Description of drawings
Fig. 1,2 is respectively the PVDF coating and contains nanometer Cr respectively
2O
3, and the condensation test experiments phenomenon of superfine cupper powder (1000 order).Fig. 3,4 is respectively the PFA modified coating surface condensation experimental phenomena that contains superfine cupper powder and SiC particle.Above modified coating surface is the high-temperaure coating of low-surface-energy owing to what use, has all showed its excellent hydrophobic property in the condensation test of steam.
Fig. 5 contains Cr
2O
3PVDF modified coating surface and the comparing result of surface heat transfer characteristic when modification not.Wherein Fig. 5 is the graph of a relation of heat transfer flux to heat transfer temperature difference (Ts-Tw) between condensing steam and the copper surface.Fig. 6 is the dropwise condensation of modified surface, the heat transfer coefficient comparative result of the membranaceous and theoretical calculating of Nusselt.Fig. 7,8 is the heat-transfer character and the surperficial comparative result that does not have modification that adds the PVDF modified coating surface of copper powder; The surface condensation form of PVDF modification is dropwise condensation (DWC), and the condensation form through modification is not film condensation (FWC).Fig. 9, the PFA modified coating modified surface heat-transfer character comparison diagram of adding copper powder; The surface condensation form of PFA modification is dropwise condensation DWC, and the condensation form through modification is not film condensation (FWC).Figure 10, the PFA modified coating surface heat transfer characteristic comparison diagram of adding SiC; The surface condensation form of PFA modification is dropwise condensation DWC, and the condensation form through modification is not film condensation (FWC).
The specific embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1:
At red copper condensation piece surface-coated PVDF modified coating, polyvinylidene fluoride resin emulsion adding mass content is 2% Cr
2O
3Nano particle, particle diameter 100～200 nanometers; 1000 purpose copper powders 2%; Through grinding 72 hours, 600 order mesh screens filter, and disperse 30 minutes with ultrasonic wave again; Aerial spraying, pressure 0.4MPa.Surface treatment process comprises oil removing, alligatoring, drying; Heat treatment process temperature-gradient method under nitrogen protection, programming rate is 3 ℃/min before 130 ℃, insulation 15min in the time of 130 ℃ guarantees that solvent volatilizees at a slow speed.Insulation 30min makes coating plastify levelling fully in the time of 280 ℃; Cooling at a slow speed, cooling velocity is 3 ℃/min, reduces internal stress between coating and matrix.
Embodiment 2:
Apply the PFA emulsion coatings at red copper surface, the CuO nano particle, mass content is 1.5%; The copper powder mass content is 3%, and granularity is less than 5 microns; Dispersant is pre-dispersed to nano particle, is stirring the PFA emulsion simultaneously with its adding.Add copper powder again after fully stirring, grind dispersion, filtration, ultrasonic wave dispersion, spraying.Heat treatment process segmentation under nitrogen protection is carried out, and room temperature to 150 ℃ speed is 3 ℃/min, and insulation 30min continues to be warming up to 380 ℃ with 5 ℃/min speed, and insulation 30min reduces to room temperature with 5 ℃/min then.
Embodiment 3:
In brass tube surface-coated PVDF coating, contain 3% copper powder particles and 2% nanometer CuO, work progress reference example 1.
Embodiment 4:
Apply the PFA coating in brass surfaces, add 2.5% superfine particulate and Cr in the coating
2O
3Nano particle, construction and heat treatment process reference example 2.
The every test index of coating of embodiment preparation sees Table 1, utilizes this coating modified condensation to show the experimental phenomena of heat transfer, sees accompanying drawing with the comparative result of film condensation heat exchange surface heat-transfer character.
Table 1. Experiment Preparation coating performance test chart
| Fluorocarbon resin | PVDF (Cu powder, Cr 2O 3) | PVDF (Cu powder, nanometer CuO) | PFA (Cu powder, nanometer CuO) | PFA (SiC powder, nanometer Cr 2O 3) |
| Coating layer thickness/(μ m) to water contact angle/(°) thermal conductivity factor/(W/m.K) | 12 86.5 0.40 | 14 84.6 0.36 | 13 114 0.42 | 10 116 0.35 |
| Adhesive force (draw circle method)/(level) pliability/(mm) resistance to impact/(kg/cm) acid and alkali resistance, salt corrosion ability | 21 30 is good | 21 30 is good | 11 50 is excellent | 11 50 is excellent |
Claims (4)
1. the preparation method of a functional heat transfer surface, utilizing the Organic fluoride carbon resin is main film forming matter, the metal and other mineral powders that add nano-powder and ultra-fine high thermal conductivity are applied on the metal heat exchange surface; The metal surface obtains having the dense coating of low-surface-energy through applying this coating after-baking after the preliminary treatment; It is characterized in that: the film forming fluorocarbon resin preferably use polytetrafluoroethylene (PTFE), tetrafluoroethene-perfluoro alkoxy ether copolymer (PFA), tetrafluoroethene-hexafluoropropylene copolymer (FEP), in one or both mix and use.
2. the preparation method of a kind of functional heat transfer surface according to claim 1, it is characterized in that: the Nano filling that adds in modified coating is metal or metal oxide, mass content is 0.5～3%.
3. the preparation method of a kind of functional heat transfer surface according to claim 1 is characterized in that: adopt superfine cupper powder, aluminium powder, nickel powder, silver powder or the inorganic oxide, the nitride that add high thermal conductivity, SiC, Si
3N
4, Al
2N
3, TiN, TiC, TiCN, Al
2O
3, CrxNy, ZrN particulate, the thickness of granularity or sheet is less than 2 microns, mass content is 5～10%.
4. the preparation method of a kind of functional heat transfer surface according to claim 1 is characterized in that: heat treatment process is that disposable thermal is handled, and heat treated temperature adopts segmentation to carry out, and coating is below 150 ℃, and programming rate is 3 ℃/min; In the time of 130～150 ℃ 1 ℃/min; In the time of 150～380 ℃ 5 ℃/min; 380～400 ℃ of insulation 30min; Slowly reduce to room temperature with 3 ℃/min speed; Heat treatment process is carried out under nitrogen protection.
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| CN101663555B (en) * | 2007-03-30 | 2012-06-13 | 西门子公司 | Coating for vapor condensers |
| CN103084321A (en) * | 2013-01-19 | 2013-05-08 | 大连理工大学 | Preparation process for nanometer perfluorocarbon composite coating |
| CN103687923A (en) * | 2011-07-29 | 2014-03-26 | W.L.戈尔有限公司 | Use of an anisotropic fluoropolymer for the conduction of heat |
| CN103909049A (en) * | 2013-01-05 | 2014-07-09 | 北京中南亚太环境科技发展有限公司 | Abrasion resistant, high temperature resistant and corrosion prevented metallic paint for air preheater and gas exchanger |
| CN104067082A (en) * | 2011-11-28 | 2014-09-24 | 阿尔法拉瓦尔股份有限公司 | Shell and tube heat exchanger with improved anti-fouling properties |
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| CN1109161A (en) * | 1994-03-21 | 1995-09-27 | 施福源 | Method and materials for manufacturing dropping condensing tubes |
| CN1077895C (en) * | 1998-11-18 | 2002-01-16 | 中国科学院昆明植物研究所 | Biological solidification technology of natural latex |
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| CN103909049A (en) * | 2013-01-05 | 2014-07-09 | 北京中南亚太环境科技发展有限公司 | Abrasion resistant, high temperature resistant and corrosion prevented metallic paint for air preheater and gas exchanger |
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| CN104774510A (en) * | 2014-12-04 | 2015-07-15 | 上海卫星装备研究所 | Antistatic thermal control coating composition, preparation method and applications thereof |
| CN104774510B (en) * | 2014-12-04 | 2017-05-03 | 上海卫星装备研究所 | Antistatic thermal control coating composition, preparation method and applications thereof |
| CN105670414A (en) * | 2016-03-18 | 2016-06-15 | 湖州国信物资有限公司 | Polytetrafluoroethylene-based composite coating and preparation method thereof |
| CN108118318B (en) * | 2016-11-28 | 2019-12-13 | 中国石油化工股份有限公司 | Nano chemical plating layer and preparation method and application thereof |
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