US20070114011A1 - Heat exchanger - Google Patents
Heat exchanger Download PDFInfo
- Publication number
- US20070114011A1 US20070114011A1 US10/580,656 US58065604A US2007114011A1 US 20070114011 A1 US20070114011 A1 US 20070114011A1 US 58065604 A US58065604 A US 58065604A US 2007114011 A1 US2007114011 A1 US 2007114011A1
- Authority
- US
- United States
- Prior art keywords
- heat exchanger
- layer
- nanoparticles
- coating
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 238000012546 transfer Methods 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005260 corrosion Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000009736 wetting Methods 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004378 air conditioning Methods 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000003049 inorganic solvent Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 48
- 238000004140 cleaning Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000006378 damage Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000009760 electrical discharge machining Methods 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000002816 gill Anatomy 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000005610 quantum mechanics Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/04—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by preventing the formation of continuous films of condensate on heat-exchange surfaces, e.g. by promoting droplet formation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
Definitions
- the invention relates to a heat exchanger with surface-treated heat transfer surfaces. It also relates to a process for the surface treatment of heat exchangers.
- a surface treatment is intended to provide the associated components with specific properties which protect them in particular from environmental influences so as to achieve improved performance and a longer service life.
- the specific application area and structural conditions need to be taken into account.
- Heat exchangers in particular evaporators, which are used in air-conditioning systems—in particular in motor vehicles—usually comprise a plurality of disks or tubes which are arranged in a row, are connected to one another in a fluid-tight manner and between which are arranged tightly packed corrugated fins.
- these allow optimum heat transfer between the refrigerant flowing through the disks or tubes and the air flowing through the network of corrugated fins, they are inevitably subject to the precipitation of condensate and dust or dirt.
- This wet, contaminated heat transfer surface offers an ideal breeding ground for microorganisms, colonization of which can lead to the formation of undesirable odors.
- corrosion damage is promoted by the wet contamination.
- the surface of an object is generally rendered hydrophobic.
- spherical drops of water form on the surface as a result of the hydrophobic configuration thereof, and these drops then run off, these surfaces are fundamentally able to repel dirt and water.
- the water drops cannot run off, on account of the very closely packed corrugated fin structure. Instead, they remain in place between the adjacent, closely packed fins and gills. Therefore, the desired self-cleaning effect by the hydrophobic configuration is in fact prevented. Moreover, this usually leads to a decrease in the overall performance of the heat exchanger.
- the hydrophilicity of a substance is characterized, inter alia, by its polarity, a low interfacial tension with respect to water and good wetability with water, which results from the fact that the adhesion forces which act between the molecules of the same substance are high at an interface compared to the cohesion forces which act between the molecules of the same substance. If a surface can be successfully wetted, a drop of liquid forms a contact angle on said surface which is less than 90°, i.e. the liquid can spread out to a greater or lesser extent on the surface. Therefore, rendering a surface hydrophilic leads to the formation of a thin, continuous film of liquid. The continuous film of liquid allows the dust and dirt particles to flow off and therefore reduces long-term accumulation of dirt and dust. Since, moreover, the corrugated fin surface dries more quickly as a result of the relatively thin film of water which is formed, the colonization of microorganisms on the heat transfer surface is also reduced.
- CN 13242732 has disclosed an aluminum heat exchanger which is provided with a layer which, inter alia, contains nanoparticles based on macromolecular surfactants and crosslinkable, unsaturated monomers and has corrosion-resistant and hydrophilic properties.
- EP 1 154 042 A1 has disclosed a heat exchanger in which the heat exchanger surface, after acid cleaning, is provided with a chromium-containing or zirconium-containing conversion layer and a hydrophilic layer based on polymer which contains silicate particles with a diameter of between 5 and 1000 nm.
- This type of coating means that compromises are generally required, and consequently, for example, optimum resistance to corrosion combined at the same time with a permanently hydrophilic surface to provide a self-cleaning action cannot be achieved with the same quality.
- the invention is based on the object of providing a heat exchanger of the above type, the heat transfer surfaces of which made from metal, in particular aluminum or aluminum compounds, are provided with a surface coating which represents an improvement on the prior art. Furthermore, it is intended to specify a process which is particularly suitable for this type of surface coating of the abovementioned heat exchanger.
- the object is achieved, according to the invention, by a plurality of layers being applied to its heat transfer surfaces, with nanoparticles being used for the coating.
- the invention is based on the consideration that the design objectives of a long service life and an improved performance, which are pursued to equal extent for the heat exchanger, cannot be achieved, or at least cannot be achieved to a satisfactory extent, by a single layer.
- design objectives which are actually divergent with respect to one another, namely for example on the one hand an optimized resistance to corrosion and on the other hand a hydrophilically configured surface.
- a hydrophilic or water-attracting and therefore wet surface fundamentally promotes damage or destruction of materials by chemical or electrochemical reactions. Therefore, to avoid corrosion, it is fundamentally desirable to suppress contact between material and water by using a hydrophobic configuration.
- a hydrophilic surface is desirable for effective self-cleaning of the heat transfer surfaces, as described above, in order to promote the formation of a thin, continuous film of liquid which allows the dust and dirt particles to flow off.
- each layer being suitable for its own specific property.
- defects in the layer can lead to the metal being exposed, and consequently this location in the metal, in particular in the case of a hydrophilic layer, i.e. a layer which attracts liquid, offers a suitable surface for attack in respect of corrosion damage.
- a hydrophilic layer i.e. a layer which attracts liquid
- offers a suitable surface for attack in respect of corrosion damage offers a suitable surface for attack in respect of corrosion damage.
- the probability that defects in the layer will lie directly above one another and expose the metal is reduced. This has a correspondingly beneficial effect with a view to reducing corrosion damage.
- tailored structures play an important role for the desired functions of the coating systems, such as for example the adhesion forces which are active between the molecules of different substances.
- the dimensions or sizes of individual components and mixtures play a crucial co-determining role in the formation of functional coatings.
- the smallest nanoparticles are clusters of a few hundred molecules and are subject to the laws of quantum mechanics, whereas for larger nanoparticles the rules of traditional solid-state physics apply.
- Nanoparticles have a greatly reduced number of structural defects than larger particles of the same chemical composition. Therefore, on account of their geometric and material-specific properties, they offer a particularly wide and versatile spectrum of actions. For this reason, nanoparticles are used for the coating.
- Nanoparticles can be produced, for example, by plasma processes, laser ablation, gas phase synthesis, sol-gel processes, spark erosion or crystallization, inter alia.
- Nanoscale particles are distinguished by a particularly large surface area/volume ratio. Because the sticking force and bonding of the particles increases with an increase in surface area, layers produced in this way are generally particularly resistant to scratching and abrasion. As a result, the surface configured in this manner does not offer any surface for attack with respect to damage to the protective coating, with the result that, for example, corrosion damage can be minimized.
- nanoscale additives which are selected to have corresponding compositions, moreover, the resistance to corrosion is improved. On account of their hydrophilicity and their relatively large surface area, these particles are hygroscopic.
- each layer of the heat exchanger preferably contains nanoparticles of different compositions.
- At least one layer to have corrosion-resistant properties and for at least one further layer to have hydrophilic and therefore self-cleaning properties.
- a corrosion-resistant layer in particular for corrosion prevention reasons, it is preferable for a corrosion-resistant layer to be applied first of all, which is advantageously followed by a hydrophilic layer.
- the hydrophilic layer preferably forms the top layer of the multiple coating.
- the layer with hydrophilic properties advantageously has a wetting contact angle with water of less than or equal to 60°, preferably of less than or equal to 40°.
- the wetting contact angle is in this case determined by what is known as the sessile drop method, which represents an optical contact angle measurement for determining the wetting properties of solids.
- the nanoparticles used for the coating are preferably formed from organic and/or inorganic compounds of aluminum, silicon, boron and/or transition metals, preferably from transition groups IV and V of the periodic system, and/or cerium dispersed and/or dissolved in inorganic and/or organic solvents.
- each layer thickness advantageously amounts to less than 1.5 ⁇ m or equal to 1.5 ⁇ m, preferably less than 1 ⁇ m or equal to 1 ⁇ m, and the total layer thickness amounts to less than 5 ⁇ m or equal to 5 ⁇ m.
- the abovementioned object is achieved by a plurality of layers being applied to a number of heat transfer surfaces made from metal, in particular from aluminum or aluminum compounds, with nanoparticles being used for the coating.
- nanoparticles of organic and/or inorganic compounds of aluminum, silicon, boron and/or transition metals preferably from transition groups IV and V of the periodic system, and/or cerium dissolved and/or dispersed in inorganic and/or organic solvents to be used for coating.
- the layers are applied by dipping, flooding or spraying, with the individual layers, in particular for particularly rapid layer build-up, being applied in direct succession, using what is known as the wet-in-wet technique, with just one drying operation.
- the individual layers are preferably applied in separate treatment steps, in each case with intermediate drying.
- the advantages achieved by the invention consist in particular in the fact that a multiple coating of heat transfer surfaces with nanoparticles used for the coating provides a heat exchanger which satisfies different and in some cases also divergent demands.
- the selected use of nanoscale particles of different materials achieves the desired functionality of the heat transfer surfaces.
- this form of surface coating it is possible, for example, to improve the resistance to corrosion or the hardness and scratch proofing, and furthermore it is possible to produce self-cleaning and antimicrobial surfaces.
- an improved self-cleaning effect brought about by rendering the heat transfer surface as hydrophilic, at least one corrosion-resistant layer and at least one further hydrophilic layer, in particular arranged thereon, are provided. Improved use and/or performance of the heat exchanger are achieved as a result of the abovementioned improved properties.
- a heat exchanger in particular an evaporator for air-conditioning systems in motor vehicles, having a double coating of its heat transfer surfaces made from aluminum substrate is provided as an exemplary embodiment.
- the nanoparticles for the respective layer are in this case produced using a sol-gel process.
- the nanoparticles of different compositions for each layer can also be produced by processes other than the sol-gel process, such as for example by the plasma process, laser ablation, gas phase synthesis, spark erosion or crystallization, inter alia.
- a first corrosion-resistant layer which is not hydrophilic, or the correspondingly configured base layer, is applied by dip coating in an organically modified inorganic sol-gel layer with water-based solvent. It is hardened by subsequent drying at a temperature in the range from 100-150° C. for 10 minutes. The layer thickness produced is less than 1 82 m.
- a further organically modified inorganic sol-gel layer with water-based solvent is applied by dip coating as the second layer or the covering layer. Its chemical composition differs from that of the layer below. The second layer or the covering layer is again hardened at 100-150° C. for 10 minutes. Its surface has a hydrophilic character and has a wetting contact angle with water of less than 40°.
- the total layer thickness of the layer structure comprising base layer and covering layer is at most 2 ⁇ m.
- the first layer or base layer ensures optimum resistance to corrosion, and the production of the functional hydrophilic covering layering improves the water run-off on the heat transfer surface. This helps dust and dirt to flow off the surface, and on account of the relatively thin film of water which is formed, faster drying of the surface is ensured. These self-cleaning and fast drying properties minimize the growth of microorganisms. All these factors improve the use properties and/or performance of heat exchangers having heat transfer surfaces which have been coated in this way.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Air-Conditioning For Vehicles (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention relates to a heat exchanger, particularly an evaporator for air conditioners in motor vehicles, having a number of heat transfer surfaces made of metal, in particular, aluminum or aluminum compounds. The aim of the invention is to provide this heat exchanger with a surface coating that is improved compared to the prior art. To this end, a number of layers are applied to its heat transfer surfaces, and nanoparticles are used for the coating.
Description
- The invention relates to a heat exchanger with surface-treated heat transfer surfaces. It also relates to a process for the surface treatment of heat exchangers.
- To satisfy industry demands imposed on components, for example those imposed by the automotive industry on heat exchangers, it is in many cases imperative that the material surfaces be treated. A surface treatment is intended to provide the associated components with specific properties which protect them in particular from environmental influences so as to achieve improved performance and a longer service life. In this context, in particular the specific application area and structural conditions need to be taken into account.
- Heat exchangers, in particular evaporators, which are used in air-conditioning systems—in particular in motor vehicles—usually comprise a plurality of disks or tubes which are arranged in a row, are connected to one another in a fluid-tight manner and between which are arranged tightly packed corrugated fins. Although these allow optimum heat transfer between the refrigerant flowing through the disks or tubes and the air flowing through the network of corrugated fins, they are inevitably subject to the precipitation of condensate and dust or dirt. This wet, contaminated heat transfer surface offers an ideal breeding ground for microorganisms, colonization of which can lead to the formation of undesirable odors. Moreover, in particular corrosion damage is promoted by the wet contamination.
- To prevent the accumulation of water and dirt on a surface, the surface of an object is generally rendered hydrophobic. On account of the fact that spherical drops of water form on the surface as a result of the hydrophobic configuration thereof, and these drops then run off, these surfaces are fundamentally able to repel dirt and water. With a hydrophobic surface of the heat exchanger described, however, the water drops cannot run off, on account of the very closely packed corrugated fin structure. Instead, they remain in place between the adjacent, closely packed fins and gills. Therefore, the desired self-cleaning effect by the hydrophobic configuration is in fact prevented. Moreover, this usually leads to a decrease in the overall performance of the heat exchanger.
- To solve this problem while maintaining the same design of heat exchanger, it is desirable for the heat transfer surfaces to be made hydrophilic.
- The hydrophilicity of a substance is characterized, inter alia, by its polarity, a low interfacial tension with respect to water and good wetability with water, which results from the fact that the adhesion forces which act between the molecules of the same substance are high at an interface compared to the cohesion forces which act between the molecules of the same substance. If a surface can be successfully wetted, a drop of liquid forms a contact angle on said surface which is less than 90°, i.e. the liquid can spread out to a greater or lesser extent on the surface. Therefore, rendering a surface hydrophilic leads to the formation of a thin, continuous film of liquid. The continuous film of liquid allows the dust and dirt particles to flow off and therefore reduces long-term accumulation of dirt and dust. Since, moreover, the corrugated fin surface dries more quickly as a result of the relatively thin film of water which is formed, the colonization of microorganisms on the heat transfer surface is also reduced.
- By way of example, CN 13242732 has disclosed an aluminum heat exchanger which is provided with a layer which, inter alia, contains nanoparticles based on macromolecular surfactants and crosslinkable, unsaturated monomers and has corrosion-resistant and hydrophilic properties.
- Furthermore, EP 1 154 042 A1 has disclosed a heat exchanger in which the heat exchanger surface, after acid cleaning, is provided with a chromium-containing or zirconium-containing conversion layer and a hydrophilic layer based on polymer which contains silicate particles with a diameter of between 5 and 1000 nm.
- This type of coating means that compromises are generally required, and consequently, for example, optimum resistance to corrosion combined at the same time with a permanently hydrophilic surface to provide a self-cleaning action cannot be achieved with the same quality.
- Consequently, the invention is based on the object of providing a heat exchanger of the above type, the heat transfer surfaces of which made from metal, in particular aluminum or aluminum compounds, are provided with a surface coating which represents an improvement on the prior art. Furthermore, it is intended to specify a process which is particularly suitable for this type of surface coating of the abovementioned heat exchanger.
- With regard to the heat exchanger, the object is achieved, according to the invention, by a plurality of layers being applied to its heat transfer surfaces, with nanoparticles being used for the coating.
- In this context, the invention is based on the consideration that the design objectives of a long service life and an improved performance, which are pursued to equal extent for the heat exchanger, cannot be achieved, or at least cannot be achieved to a satisfactory extent, by a single layer. This applies in particular to design objectives which are actually divergent with respect to one another, namely for example on the one hand an optimized resistance to corrosion and on the other hand a hydrophilically configured surface. For example, a hydrophilic or water-attracting and therefore wet surface fundamentally promotes damage or destruction of materials by chemical or electrochemical reactions. Therefore, to avoid corrosion, it is fundamentally desirable to suppress contact between material and water by using a hydrophobic configuration. On the other hand, a hydrophilic surface is desirable for effective self-cleaning of the heat transfer surfaces, as described above, in order to promote the formation of a thin, continuous film of liquid which allows the dust and dirt particles to flow off.
- To satisfy a plurality of, often contradictory, design objectives, therefore, a multiple coating is provided, each layer being suitable for its own specific property. Specifically, with one layer, defects in the layer can lead to the metal being exposed, and consequently this location in the metal, in particular in the case of a hydrophilic layer, i.e. a layer which attracts liquid, offers a suitable surface for attack in respect of corrosion damage. In the case of a plurality of layers, the probability that defects in the layer will lie directly above one another and expose the metal is reduced. This has a correspondingly beneficial effect with a view to reducing corrosion damage.
- With regard to the materials used for the layers, tailored structures play an important role for the desired functions of the coating systems, such as for example the adhesion forces which are active between the molecules of different substances. The dimensions or sizes of individual components and mixtures play a crucial co-determining role in the formation of functional coatings. Particularly small particles, in particular with a size of a few millionths of a millimeter, are known as nanoparticles. The smallest nanoparticles are clusters of a few hundred molecules and are subject to the laws of quantum mechanics, whereas for larger nanoparticles the rules of traditional solid-state physics apply. Nanoparticles have a greatly reduced number of structural defects than larger particles of the same chemical composition. Therefore, on account of their geometric and material-specific properties, they offer a particularly wide and versatile spectrum of actions. For this reason, nanoparticles are used for the coating.
- Nanoparticles can be produced, for example, by plasma processes, laser ablation, gas phase synthesis, sol-gel processes, spark erosion or crystallization, inter alia.
- Nanoscale particles are distinguished by a particularly large surface area/volume ratio. Because the sticking force and bonding of the particles increases with an increase in surface area, layers produced in this way are generally particularly resistant to scratching and abrasion. As a result, the surface configured in this manner does not offer any surface for attack with respect to damage to the protective coating, with the result that, for example, corrosion damage can be minimized. By using nanoscale additives which are selected to have corresponding compositions, moreover, the resistance to corrosion is improved. On account of their hydrophilicity and their relatively large surface area, these particles are hygroscopic. Consequently, their surface is wet and provides a thin film of liquid, which both allows the dirt and dust particles to flow off and also prevents the colonization of microorganisms as a result of the rapid drying of the thin film of liquid. Therefore, each layer of the heat exchanger preferably contains nanoparticles of different compositions.
- To ensure improved performance and a longer service life of the heat exchanger, it is preferable for at least one layer to have corrosion-resistant properties and for at least one further layer to have hydrophilic and therefore self-cleaning properties.
- In a particularly advantageous configuration, in particular for corrosion prevention reasons, it is preferable for a corrosion-resistant layer to be applied first of all, which is advantageously followed by a hydrophilic layer. To ensure that a particularly effective self-cleaning effect is achieved, the hydrophilic layer preferably forms the top layer of the multiple coating. The layer with hydrophilic properties advantageously has a wetting contact angle with water of less than or equal to 60°, preferably of less than or equal to 40°. The wetting contact angle is in this case determined by what is known as the sessile drop method, which represents an optical contact angle measurement for determining the wetting properties of solids.
- In a particularly advantageous configuration of the heat transfer surfaces, it is expedient to use chromium-free, nontoxic additives for the surface coating. For this purpose, the nanoparticles used for the coating are preferably formed from organic and/or inorganic compounds of aluminum, silicon, boron and/or transition metals, preferably from transition groups IV and V of the periodic system, and/or cerium dispersed and/or dissolved in inorganic and/or organic solvents.
- For the heat exchanger to be used in air-conditioning systems, in particular in motor vehicles, for efficiency reasons it is expedient to provide a particularly thin coating which does not lead to any significant increase in volume and weight. Therefore, each layer thickness advantageously amounts to less than 1.5 μm or equal to 1.5 μm, preferably less than 1 μm or equal to 1 μm, and the total layer thickness amounts to less than 5 μm or equal to 5 μm.
- With regard to the process for the surface treatment of heat exchangers, the abovementioned object is achieved by a plurality of layers being applied to a number of heat transfer surfaces made from metal, in particular from aluminum or aluminum compounds, with nanoparticles being used for the coating.
- In this case, it is advantageous for nanoparticles of organic and/or inorganic compounds of aluminum, silicon, boron and/or transition metals, preferably from transition groups IV and V of the periodic system, and/or cerium dissolved and/or dispersed in inorganic and/or organic solvents to be used for coating.
- It is advantageous for the layers to be applied by dipping, flooding or spraying, with the individual layers, in particular for particularly rapid layer build-up, being applied in direct succession, using what is known as the wet-in-wet technique, with just one drying operation.
- In an alternative configuration of the process, the individual layers are preferably applied in separate treatment steps, in each case with intermediate drying.
- The advantages achieved by the invention consist in particular in the fact that a multiple coating of heat transfer surfaces with nanoparticles used for the coating provides a heat exchanger which satisfies different and in some cases also divergent demands. The selected use of nanoscale particles of different materials achieves the desired functionality of the heat transfer surfaces. With this form of surface coating it is possible, for example, to improve the resistance to corrosion or the hardness and scratch proofing, and furthermore it is possible to produce self-cleaning and antimicrobial surfaces. For both an improved resistance to corrosion and at the same time also an improved self-cleaning effect brought about by rendering the heat transfer surface as hydrophilic, at least one corrosion-resistant layer and at least one further hydrophilic layer, in particular arranged thereon, are provided. Improved use and/or performance of the heat exchanger are achieved as a result of the abovementioned improved properties.
- A heat exchanger, in particular an evaporator for air-conditioning systems in motor vehicles, having a double coating of its heat transfer surfaces made from aluminum substrate is provided as an exemplary embodiment. The nanoparticles for the respective layer are in this case produced using a sol-gel process.
- Of course, depending on the desired profile of requirements, it is also possible for a multiple coating to be applied to the heat transfer surfaces, and of course the nanoparticles of different compositions for each layer can also be produced by processes other than the sol-gel process, such as for example by the plasma process, laser ablation, gas phase synthesis, spark erosion or crystallization, inter alia.
- In the exemplary embodiment, a first corrosion-resistant layer, which is not hydrophilic, or the correspondingly configured base layer, is applied by dip coating in an organically modified inorganic sol-gel layer with water-based solvent. It is hardened by subsequent drying at a temperature in the range from 100-150° C. for 10 minutes. The layer thickness produced is less than 1 82 m. A further organically modified inorganic sol-gel layer with water-based solvent is applied by dip coating as the second layer or the covering layer. Its chemical composition differs from that of the layer below. The second layer or the covering layer is again hardened at 100-150° C. for 10 minutes. Its surface has a hydrophilic character and has a wetting contact angle with water of less than 40°. This hydrophilicity is durable even under long-term action of condensation water, so that the contact angle is still below 40° even after condensation water exposure for over 1000 hours in accordance with the condensation water constant climate test in accordance with DIN 50017-KK. The total layer thickness of the layer structure comprising base layer and covering layer is at most 2 μm.
- Therefore, the first layer or base layer ensures optimum resistance to corrosion, and the production of the functional hydrophilic covering layering improves the water run-off on the heat transfer surface. This helps dust and dirt to flow off the surface, and on account of the relatively thin film of water which is formed, faster drying of the surface is ensured. These self-cleaning and fast drying properties minimize the growth of microorganisms. All these factors improve the use properties and/or performance of heat exchangers having heat transfer surfaces which have been coated in this way.
Claims (10)
1. A heat exchanger, in particular an evaporator for air-conditioning systems in motor vehicles, having a number of heat transfer surfaces made from metal, in particular aluminum or aluminum compounds, to which a plurality of layers have been applied, nanoparticles being used for the coating.
2. The heat exchanger as claimed in claim 1 , in which each layer contains nanoparticles of different compositions.
3. The heat exchanger as claimed in claim 1 , in which at least one layer has corrosion-resistant properties and at least one further layer, preferably arranged thereon, has hydrophilic properties.
4. The heat exchanger as claimed in claim 3 , in which the layer with hydrophilic properties has a wetting contact angle with water of less than or equal to 60°, preferably of less than or equal to 40°.
5. The heat exchanger as claimed in claim 1 , in which the nanoparticles of organic and/or inorganic compounds of aluminum, silicon, boron and/or transition metals, preferably from transition groups IV and V of the periodic system, and/or cerium dissolved and/or dispersed in inorganic and/or organic solvents are used for the coating.
6. The heat exchanger as claimed in claim 1 , in which each layer thickness amounts to less than 1.5 μm or equal to 1.5 μm, preferably less than 1 μm or equal to 1 μm, and in which the total layer thickness amounts to less than 5 μm or equal to 5 μm.
7. A process for the surface treatment of heat exchangers, in particular as claimed in claim 1 , in which a plurality of layers are applied to a number of heat transfer surfaces made from metal, in particular aluminum or aluminum compounds, with nanoparticles being used for the coating.
8. The process as claimed in claim 7 , in which the nanoparticles of organic and/or inorganic compounds of aluminum, silicon, boron and/or transition metals, preferably from transition groups IV and V of the periodic system, and/or cerium dispersed and/or dissolved in inorganic and/or organic solvents are used for the coating.
9. The process as claimed in claim 7 , in which the layers are applied by dipping, flooding or spraying, with the individual layers being applied in direct succession without any intermediate drying.
10. The process as claimed in claim 7 , in which the layers are applied by dipping, flooding or spraying, with the individual layers being applied in separate treatment steps in each case with intermediate drying.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10355833A DE10355833A1 (en) | 2003-11-26 | 2003-11-26 | heat exchangers |
| DE10355833.0 | 2003-11-26 | ||
| PCT/EP2004/012783 WO2005052489A2 (en) | 2003-11-26 | 2004-11-11 | Heat exchanger |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20070114011A1 true US20070114011A1 (en) | 2007-05-24 |
Family
ID=34609389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/580,656 Abandoned US20070114011A1 (en) | 2003-11-26 | 2004-11-11 | Heat exchanger |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20070114011A1 (en) |
| EP (1) | EP1690058B1 (en) |
| JP (1) | JP2007512493A (en) |
| AT (1) | ATE552471T1 (en) |
| DE (1) | DE10355833A1 (en) |
| WO (1) | WO2005052489A2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060162817A1 (en) * | 2003-06-25 | 2006-07-27 | Snjezana Boger | Fluxing agent for soldering metal components |
| US20080245512A1 (en) * | 2005-09-14 | 2008-10-09 | Behr Gmbh & Co., Kg | Heat Exchanger, In Particular Exhaust Gas Heat Exchanger |
| US20100199687A1 (en) * | 2009-02-11 | 2010-08-12 | Marlow Industries, Inc. | Temperature control device |
| US20100206527A1 (en) * | 2009-02-18 | 2010-08-19 | Hu Lin-Wen | In-Situ Treatment of Metallic Surfaces |
| US20120181004A1 (en) * | 2011-01-13 | 2012-07-19 | Samsung Electronics Co., Ltd. | Surface coating layer and heat exchanger including the surface coating layer |
| US9851161B2 (en) | 2012-01-03 | 2017-12-26 | Lockheed Martin Corporation | Heat exchanger construction using low temperature sinter techniques |
| WO2018067679A1 (en) * | 2016-10-04 | 2018-04-12 | 3M Innovative Properties Company | Methods of making and using heat exchangers |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005023771A1 (en) * | 2005-05-19 | 2006-11-23 | R. Scheuchl Gmbh | Heat exchanger has surfaces of walls provided with coating of dirt deflecting particles in nano-range |
| DE102006030199A1 (en) * | 2006-06-30 | 2008-01-03 | Klingenburg Gmbh | Moisture and / or heat exchange device, e.g. Plate heat exchanger, sorption rotor, Adsorptionsentfeuchtungsrotor or the like. |
| DE102006055755B4 (en) * | 2006-09-18 | 2008-12-24 | Fpe Fischer Gmbh | Housing for an electrical device and electrical device with it |
| DE102009013054A1 (en) * | 2009-03-16 | 2010-09-23 | Behr Gmbh & Co. Kg | heat exchangers |
| SA111320468B1 (en) * | 2010-05-26 | 2015-04-01 | الفا لافال كوربوريت ايه بي | Heat exchanger plates with anti-fouling properties |
| DE102012101980A1 (en) * | 2012-03-08 | 2013-09-12 | Alpha-Innotec Gmbh | Vaporizer for refrigerant circuit in air and/or water heat pump heating system for heating e.g. industrial water, has nano-coating coated on outer surface of vaporizer, where ice is set on region of vaporizer in normal operation condition |
| JP6485714B2 (en) * | 2017-06-06 | 2019-03-20 | パナソニックIpマネジメント株式会社 | Heat exchanger with antifouling coating film |
| US20200166299A1 (en) * | 2017-07-27 | 2020-05-28 | Oxford Nanosytems LTD | Heat Exchange Element and Process for Production |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020107133A1 (en) * | 2000-05-19 | 2002-08-08 | Tomasz Troczynski | Process for making chemically bonded composite hydroxide ceramics |
| US20030092812A1 (en) * | 2000-01-17 | 2003-05-15 | Kazuya Nakada | Treating agent for imparting hydrophilicity and high corrosion resistance, hydrophilizing fluid, and method of hydrophilizing |
| US6571864B1 (en) * | 1998-12-04 | 2003-06-03 | Samsung Electronics Co., Ltd. | Antibacterial and antifungal aluminum alloy fin material and a heat exchanger provided therewith for use in an air conditioner |
| US6659171B2 (en) * | 2001-03-27 | 2003-12-09 | Nippon Paint Co., Ltd. | Hydrophilic modification method and heat exchanger treated thereby |
| US20050176851A1 (en) * | 2002-06-12 | 2005-08-11 | Cook Ronald L. | Releasable corrosion inhibitor compositions |
| US7077891B2 (en) * | 2002-08-13 | 2006-07-18 | Air Products And Chemicals, Inc. | Adsorbent sheet material for parallel passage contactors |
| US7416781B2 (en) * | 2002-05-11 | 2008-08-26 | Basf Coatings Ag | Coatings, methods for producing the same, and the use thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS582596A (en) * | 1981-06-30 | 1983-01-08 | Nippon Parkerizing Co Ltd | Surface treatment method for aluminum heat exchanger |
| JPS59205596A (en) * | 1983-05-04 | 1984-11-21 | Showa Alum Corp | Aluminum fin for heat exchanger |
| JPS59229197A (en) * | 1983-06-08 | 1984-12-22 | Nippon Parkerizing Co Ltd | Surface treatment procedure for aluminum heat exchanger |
| JPH01208478A (en) * | 1988-02-15 | 1989-08-22 | Furukawa Alum Co Ltd | Production of precoated fin material for heat exchanger |
| DE19520401C1 (en) * | 1995-03-30 | 1996-08-01 | Norbert Dipl Ing Taufenbach | Heat exchanger for heat conducting component in pump and/or resonator region of solid state power laser |
| JPH10220978A (en) * | 1997-02-07 | 1998-08-21 | Matsushita Refrig Co Ltd | Fin and tube type heat exchanger |
| JP4183150B2 (en) * | 1999-04-21 | 2008-11-19 | 住友軽金属工業株式会社 | Aluminum alloy clad material for heat exchangers with excellent erosion and corrosion resistance |
| JP4008620B2 (en) * | 1999-06-04 | 2007-11-14 | カルソニックカンセイ株式会社 | Aluminum alloy heat exchanger |
| EP1143206A3 (en) * | 2000-04-03 | 2003-05-02 | VTH Verfahrentechnik für Heizung AG | Heat exchanger for boiler or instantaneous heater |
| DE10045606A1 (en) * | 2000-09-15 | 2002-03-28 | Volkswagen Ag | Oligodynamic coating for the inner metallic surfaces of automobile air conditioners comprises matrix based on (hetero)-polysiloxanes, nano-scale heavy metal particles and an optional corrosion inhibitor |
| DE10207671B4 (en) * | 2002-02-22 | 2004-01-22 | M.Pore Gmbh | heat exchangers |
| DE10213756A1 (en) * | 2002-03-26 | 2003-10-09 | Behr Gmbh & Co | Cooling circuit or component, comprises a coating composed of an organic hybrid material in the areas exposed to coolant |
| DE10327365B4 (en) * | 2003-06-16 | 2007-04-12 | AHC-Oberflächentechnik GmbH & Co. OHG | An article with a corrosion protection layer and its use |
-
2003
- 2003-11-26 DE DE10355833A patent/DE10355833A1/en not_active Withdrawn
-
2004
- 2004-11-11 JP JP2006540259A patent/JP2007512493A/en active Pending
- 2004-11-11 US US10/580,656 patent/US20070114011A1/en not_active Abandoned
- 2004-11-11 AT AT04803126T patent/ATE552471T1/en active
- 2004-11-11 EP EP04803126A patent/EP1690058B1/en not_active Expired - Lifetime
- 2004-11-11 WO PCT/EP2004/012783 patent/WO2005052489A2/en not_active Ceased
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6571864B1 (en) * | 1998-12-04 | 2003-06-03 | Samsung Electronics Co., Ltd. | Antibacterial and antifungal aluminum alloy fin material and a heat exchanger provided therewith for use in an air conditioner |
| US20030092812A1 (en) * | 2000-01-17 | 2003-05-15 | Kazuya Nakada | Treating agent for imparting hydrophilicity and high corrosion resistance, hydrophilizing fluid, and method of hydrophilizing |
| US20020107133A1 (en) * | 2000-05-19 | 2002-08-08 | Tomasz Troczynski | Process for making chemically bonded composite hydroxide ceramics |
| US6659171B2 (en) * | 2001-03-27 | 2003-12-09 | Nippon Paint Co., Ltd. | Hydrophilic modification method and heat exchanger treated thereby |
| US7416781B2 (en) * | 2002-05-11 | 2008-08-26 | Basf Coatings Ag | Coatings, methods for producing the same, and the use thereof |
| US20050176851A1 (en) * | 2002-06-12 | 2005-08-11 | Cook Ronald L. | Releasable corrosion inhibitor compositions |
| US7077891B2 (en) * | 2002-08-13 | 2006-07-18 | Air Products And Chemicals, Inc. | Adsorbent sheet material for parallel passage contactors |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060162817A1 (en) * | 2003-06-25 | 2006-07-27 | Snjezana Boger | Fluxing agent for soldering metal components |
| US8002905B2 (en) * | 2003-06-25 | 2011-08-23 | Behr Gmbh & Co. Kg | Fluxing agent for soldering metal components |
| US8557055B2 (en) | 2003-06-25 | 2013-10-15 | Behr Gmbh & Co. Kg | Fluxing agent for soldering metal components |
| US20080245512A1 (en) * | 2005-09-14 | 2008-10-09 | Behr Gmbh & Co., Kg | Heat Exchanger, In Particular Exhaust Gas Heat Exchanger |
| US20100199687A1 (en) * | 2009-02-11 | 2010-08-12 | Marlow Industries, Inc. | Temperature control device |
| US8359871B2 (en) * | 2009-02-11 | 2013-01-29 | Marlow Industries, Inc. | Temperature control device |
| US20100206527A1 (en) * | 2009-02-18 | 2010-08-19 | Hu Lin-Wen | In-Situ Treatment of Metallic Surfaces |
| US20120181004A1 (en) * | 2011-01-13 | 2012-07-19 | Samsung Electronics Co., Ltd. | Surface coating layer and heat exchanger including the surface coating layer |
| US9851161B2 (en) | 2012-01-03 | 2017-12-26 | Lockheed Martin Corporation | Heat exchanger construction using low temperature sinter techniques |
| WO2018067679A1 (en) * | 2016-10-04 | 2018-04-12 | 3M Innovative Properties Company | Methods of making and using heat exchangers |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE552471T1 (en) | 2012-04-15 |
| WO2005052489A2 (en) | 2005-06-09 |
| DE10355833A1 (en) | 2005-06-23 |
| JP2007512493A (en) | 2007-05-17 |
| EP1690058A2 (en) | 2006-08-16 |
| EP1690058B1 (en) | 2012-04-04 |
| WO2005052489A3 (en) | 2005-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20070114011A1 (en) | Heat exchanger | |
| KR940007204B1 (en) | heat transmitter | |
| EP2119996B1 (en) | Aluminum fin material for heat exchanger | |
| EP2977417B1 (en) | Hydrophilic surface treatment agent for aluminum-containing metal heat exchangers having excellent drainage | |
| US20230031778A1 (en) | Selectively Applied Gradient Coating Compositions | |
| JP5859895B2 (en) | Aluminum fin material | |
| JP2010223520A (en) | Aluminum fin material for heat exchanger | |
| JP7601731B2 (en) | Aluminum fin material | |
| US7927707B2 (en) | Plate material and manufacturing method thereof | |
| JP3430482B2 (en) | Heat exchange material | |
| JP5643500B2 (en) | Aluminum fin material for heat exchanger | |
| JP3383914B2 (en) | Aluminum fin material for heat exchanger | |
| WO2022130620A1 (en) | Heat exchanger and method for manufacturing heat exchanger | |
| CN1431454A (en) | Aluminium alloy material with coated film and heat exchanger radiating fin made by same material | |
| JP3717205B2 (en) | Aluminum-containing metal heat exchanger and manufacturing method | |
| WO2021153495A1 (en) | Aluminum fin material, heat exchanger, air conditioner, and method for producing aluminum fin material | |
| JP7502232B2 (en) | Aluminum fin material | |
| JP2000256579A (en) | Hydrophilic coating composition and hydrophilic coating comprising the composition | |
| JP7609712B2 (en) | Aluminum fin material and frost inhibitor | |
| JP5532022B2 (en) | Painted steel plate | |
| JPH10168381A (en) | Highly hydrophilic paint | |
| JP2008164238A (en) | Aluminum fin material for heat exchanger and heat exchanger using the same | |
| JP5478330B2 (en) | Alkali-resistant aluminum fin material for heat exchanger and heat exchanger | |
| WO2021162061A1 (en) | Aluminum fin material, heat exchanger, and method for producing aluminum fin material | |
| JP2000256580A (en) | Hydrophilic coating composition and hydrophilic coating comprising the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: BEHR GMBH & CO. KG, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MAMBER, OLIVER;REEL/FRAME:018267/0299 Effective date: 20060903 |
|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |