CN104067082A - Shell and tube heat exchanger with improved anti-fouling properties - Google Patents

Shell and tube heat exchanger with improved anti-fouling properties Download PDF

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Publication number
CN104067082A
CN104067082A CN201280058344.7A CN201280058344A CN104067082A CN 104067082 A CN104067082 A CN 104067082A CN 201280058344 A CN201280058344 A CN 201280058344A CN 104067082 A CN104067082 A CN 104067082A
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China
Prior art keywords
shell
coating
tube
tube exchanger
pipe
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CN201280058344.7A
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Chinese (zh)
Inventor
T·斯文森
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Alfa Laval AB
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Alfa Laval AB
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Publication of CN104067082A publication Critical patent/CN104067082A/en
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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
    • 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
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
    • 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
    • F28F13/06—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by affecting the pattern of flow of the heat-exchange media
    • F28F13/12—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by affecting the pattern of flow of the heat-exchange media by creating turbulence, e.g. by stirring, by increasing the force of circulation

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)

Abstract

A shell and tube heat exchanger (1) comprising a shell (2) having an inlet end- cap (3) attached to a first end (4) of the shell (2), wherein an outlet end-cap (5) is attached to a second end (6) of the shell (2) and a tube bundle (7) being housed within the shell (2), said tube bundle (7) including a plurality of parallel-spaced tubes (8) that traverse the interior of shell (2) from a first end to a second end of the tube bundle, and wherein a plurality of baffles (11) are arranged within the shell (2) supporting the parallel-spaced tubes (8) of the tube bundle (7). At least a part of the shell and tube heat exchanger is provided with a coating comprising silicon oxide, SiOx.

Description

The shell and tube exchanger with improved antifouling property
Technical field
The present invention relates generally to shell and tube exchanger (shell and tube heat exchanger), and the heat transfer between two kinds of fluids of its permission different temperatures is for various objects.Especially, the present invention relates to shell and tube exchanger, it is coated for improvement of antifouling property, and has in certain embodiments predetermined architectural characteristic, for guaranteeing that coating protection is held in shell and tube exchanger in use.
Background technology
In many industrial process, the pollution of heat-transfer equipment is a problem.In order to make to keep gratifying performance in the routine work of equipment, clean to it is necessary with the sedimental accumulation that removes on heating surface.The deposit for example fluid from equipment, growth of microorganism and/or rubbish produces.
Shell and tube exchanger can be polluted along with the time, and it causes the heat transfer that weakens and the pressure drop of increase, and the performance that therefore causes the integral body of heat exchanger to reduce.Depend on the fluid for example using, heat exchanger may be subject to severe contamination and be difficult to clean, therefore in order to recover the performance of heat exchanger, at the mechanical cleaning that needs strong washing agent and/or brute force suitable period through.Clean not only elapsed time but also cost are high.In addition, during described cleaning, the associated process of shell and tube exchanger may must be closed.
Shell and tube exchanger is made by the metal with high surface free energy, and this causes most of fluids easily to infiltrate surface.
In addition, when manufacturing heat exchanger surface, the forming operation of metal has increased surface roughness, and this is conventionally relevant to the accumulation faster of marine sediments.
GB2428604 discloses provides coating to pollute to reduce on shell and tube exchanger.
US20080073063 discloses a kind of shell and tube exchanger, and it scribbles low-surface-energy material, to reduce pollution.
For the time that guarantees that operation of heat exchanger is longer, need to find new approach with guarantee heat exchanger and surface compared with of low pollution.Meanwhile, the shut-in time that shortens the process relate to shell and tube exchanger is required.
The problem that at present known nonpolluting coating faces is, in the wearability of difference of application floating coat of using the heat transferring medium of abrasion, the heat transferring medium of this abrasion is sand or other granular materials for example, and it enters shell and tube exchanger together with heat exchanging fluid.In addition,, owing to acting on moment of torsion and the tension force of shell and tube exchanger in application under high pressure, may there is coating crack.
Summary of the invention
An object of the present invention is to provide the improvement surface for shell and tube exchanger, when using in shell and tube exchanger, it reduces surperficial pollution.Another object is to make the surface of shell and tube exchanger have antifouling property, and it is wear-resisting under abrasive environment, and has the high-wearing feature that opposing crackle forms.
This object realizes by following shell and tube exchanger, it comprises housing, the import end cap with the first end that is attached to housing, wherein export the second end that end cap is attached to housing, tube bank is contained in housing, and described tube bank comprises the pipe of a plurality of parallel interval, and its first end from tube bank traverses the inside of housing to the second end, wherein a plurality of baffle plates are arranged in housing, thereby support the pipe of the parallel interval of tube bank.Shell and tube exchanger has the Si oxide of comprising SiO xcoating, it has the atomic ratio of O/Si > 1, carbon content>=10 atom %, and the coating layer thickness of about 1-30 μ m, this coating is made by sol-gel (sol-gel) method, and is applied at least a portion on shell and tube exchanger surface.
According to a further aspect in the invention, the bed thickness of the described coating on shell and tube exchanger is 5-30 μ m, preferably 2-20 μ m.
In accordance with a further aspect of the present invention, comprise Si oxide SiO xcoating there is O/Si>=1.5-3, the atomic ratio of O/Si>=2-2.5 preferably.
According to another aspect of the invention, composition has carbon content >=20-60 atom %, preferably >=30-40 atom %.
The advantage of this shell and tube exchanger is, reduces significantly surperficial pollution.By the coating composition that comprises the sol-gel material with organo-silicon compound is applied to shell and tube exchanger surface, surface free energy and roughness have all reduced, thereby cause pollution minimizing and the portable cleaning on shell and tube exchanger surface.And, the shell and tube exchanger surface display that is coated with sol-gel of the present invention superior wearability, and there is flexibility, it has reduced the risk that produces crack in coating.In addition, by shell and tube exchanger according to the present invention, can reduce the overall dimensions of heat exchanger, and keep the heat-transfer capability of shell and tube exchanger.
Accompanying drawing explanation
Further object of the present invention, feature and advantage are manifested by the following detailed description of different embodiments of the invention with reference to appended schematic diagram, wherein
Fig. 1 is the schematic diagram according to shell and tube exchanger of the present invention;
Fig. 2 is the surperficial schematic section that has the shell and tube exchanger of nonpolluting coating according to of the present invention.
The specific embodiment
Fig. 1 is the side view of the shell and tube exchanger 1 that arranges according to a preferred embodiment of the invention.Shell and tube exchanger 1 comprises housing 2, and it has the import end cap 3 of the first end 4 that is attached to housing 2.Outlet end cap 5 is attached to the second end 6 of housing 2.
The part being broken away of housing 2 has disclosed the tube bank 7 being contained in housing 2.Tube bank 7 comprises the pipe 8 of a plurality of parallel interval, and its first end from tube bank traverses the inside of housing 2 to the second end.A plurality of baffle plates 11 are arranged in housing 2 and support the pipe 8 of the parallel interval of tube bank 7.
In operation, the first heat exchanging fluid, such as flue gas or carry thermal medium of used heat etc., is introduced into housing 2 by import.The first heat exchanging fluid traverses housing 2 by the path being formed by baffle plate, and leaves housing 2 by outlet.Treat by import, to enter import end cap 3 at interior heated the second heat exchanging fluid of heat exchanger 1.The second heat exchanging fluid enters tube bank 7 and by the pipe 8 of parallel interval, is passed the first heat exchanging fluid heating of the shell-side of heat exchanger 1 simultaneously.The second heat exchanging fluid finally flows to outlet end cap 5 from restraining 7, and leaves heat exchanger 1 by outlet.
Coating used according to the invention can be called as non-sticking lining, and it makes the surface of the shell and tube exchanger of pollution easy to clean.Coating surface according to the present invention than traditional shell and tube exchanger surface along with the time has been shown good heat transfer faster because the latter is subject to polluting, thereby reduced to a greater degree heat transfer property.The coating on surface also causes more smooth surface, thereby causes better flow behavior.Than traditional shell pipe heat exchanger, pressure drop for shell and tube exchanger according to the present invention also along with the time reduces, because the accumulation of impurity, microorganism and other materials is not obvious.
Coated shell and tube exchanger according to the present invention is easy to clean, only need make water carry out high-pressure wash.For surface according to the present invention, do not need a large amount of mechanical cleanings consuming time or use strong acid, alkali or washing agent for example NaOH and HNO 3clean.
According to the present invention, the surface of shell and tube exchanger is used sol-gel process to be coated with the composition that includes organic silicon compound.Organo-silicon compound are the raw material that use in sol-gel process, and are preferably silane oxo-compound.In sol-gel process, colloidal sol is converted into gel with production nano material.By hydrolysis and condensation reaction, in liquid, produce the three-dimensional network of interlayer molecules.Heat treatment stages is for being further processed as gel nano material or nanostructured to form final coating.The coating that comprises described nano material or nanostructured mainly comprises Si oxide SiOx, and it has the atomic ratio of O/Si > 1, preferably the atomic ratio of O/Si >=1.5-3, more preferably O/Si >=2-2.5.Preferred Si oxide is silica SiO 2.Si oxide forms three-dimensional network, and it has the superior adherence of effects on surface.
Coating of the present invention further has the carbon content for example existing in hydrocarbon chain.Hydrocarbon can have or can not have the functional group for example existing, such as C=O, C-O, C-O-C, C-N, N-C-O, N-C=O etc. in hydrocarbon chain or aryl.Preferably, carbon content >=10 atom %, preferably >=20-60 atom %, most preferably >=30-40 atom %.Hydrocarbon provides flexibility and elasticity for coating.Hydrocarbon chain is hydrophobic and oleophobic, and it causes the sticky characteristic of coating.
Figure 2 illustrates for thering is the schematic diagram on surface 9 of the shell and tube exchanger of Si oxide sol-gel coating 10.Between 9 self and the coating Si oxides of surface, be interface 11 between coating siloxanes and the metal oxide film on surface 9.The coated body of following described interface is the siloxane network 12 with organic connection chain and hole, and it provides elasticity for coating.Outermost layer is functional surface 13, for reduce pollution hydrophobic/oleophobic surface.
By the combination of durable and flexible coating, realized the surface for shell and tube exchanger, it has superior not viscosity, and wear-resistant and cracking resistance.When relative to each other move on surface, the flexible particular importance of coating is to avoid the cracking of coating.
In one embodiment of the invention, at least one colloidal sol that includes organic silicon compound is for coated surface.Surface can be soaked/apply with colloidal sol in any suitable method.For face coat, preferably by spraying, flooding or flood, apply.At least a portion of one side on shell and tube exchanger surface is by coated.Alternatively, between the operating period in shell and tube exchanger, at least one side on all surface with fluid contact or surface is coated.And at least one side on shell and tube exchanger surface can be applied completely.Alternatively, the both sides of pipe can be all coated.If both sides are coated, they can partly or wholly be applied with any combination so.Certainly, than will more surface can be coated with the surface of fluid contact.Preferably, coated with all surface of fluid contact that causes pollution.
In another embodiment, method comprise Tube Sheet of Heat Exchanger at least by the surperficial pretreatment being applied by least one colloidal sol.This pretreatment also preferably by dipping, flood or spray enforcement.This pretreatment is for cleaning by coated surface, so that coating afterwards has better adhesiveness in Tube Sheet of Heat Exchanger.Like this pretreated be exemplified as use acetone and/or alkaline solution for example caustic solution process.
In another embodiment, method comprises heat treatment stages, for example, can after pretreatment, implement drying process, and is utilizing described colloidal sol to carry out after practical coating pipe, dry and/or curing operation is normally necessary.Coating preferably use traditional heating device for example baking box heat.
Comprise SiO xcomposition be applied to the surface for shell and tube exchanger.Applying by sol-gel process of this composition implemented.The thickness of the film obtaining of lip-deep described composition is preferably 1-30 μ m.The thickness of coat film is important for the use in shell and tube exchanger.Film thickness be less than 1 μ m be considered to be not enough to wear-resisting because the surface of shell and tube exchanger in use relative to each other can be moved slightly.This slight motion causes the wearing and tearing of film, through coating after a period of time, will be worn away.The thickness of film also has the upper limit, because the heat transfer of exerting one's influence of the material on heating surface, and therefore affects the performance of shell and tube exchanger.The upper limit of the film applying is preferably 30 μ m.Therefore, the film thickness of the composition that comprises Si oxide colloidal sol is 1-30 μ m, 1.5-25 μ m preferably, 2-20 μ m preferably, 2-15 μ m preferably, preferably 2-10 μ m and preferably 3-10 μ m.
For surperficial base material, can be selected from several metals and metal alloy.Preferably, base material is selected from titanium, nickel, copper, aforesaid any alloy, stainless steel and/or carbon steel.Yet titanium, aforesaid any alloy or stainless steel are preferred.
From description above, although described and shown various embodiment of the present invention, the present invention is not limited to this, but the present invention also can otherwise implement in the scope that limits theme in the claims.
example
In order to study long offshore set-up of operating time, therefore on low-surface-energy glass ceramic coating, test.
To two low-surface-energy glass ceramic coatings, coating 1 and coating 2 are tested, and result is as follows.Coating 1 is sila (Silan) terminated polymer in butyl acetate, and coating 2 is the polysiloxanes-urethane resins in solvent naphtha/butyl acetate.
stage A
The following character of coating has been recorded in analysis, relates to that base material soaks and adhesion, contact angle, coating layer thickness and for 1.2% HNO 3at H 2in O, 1% NaOH is at H 2in O and the stability of crude oil.Result is summarized as follows table 1.
Table 1
In the time of on spraying to stainless steel or titanium base material, two coatings have all shown superior soaking.
According to DIN EN ISO 2409, adhesion decides by the test of crosscut/tape.Grade is from 0 (superior) to 5 (extreme differences).0 or 1 is acceptable, and 2-5 is unacceptable.Grade after the first numeral crosscut (1mm grid), the second numeral provides the grading applying after tape is also taken away again.
In order to obtain coating 1 and the best adhesion of coating 2, base material needs pretreatment.
In order to obtain the preferably adhesion of coating 1 on stainless steel, base material must carry out pretreatment.Base material is immersed in alkaline cleaner to 30 minutes.Then base material water and demineralized water are cleaned, and before applying coating 1 half an hour with inner drying to reach best adhesion.If test only shows, with acetone, implement the cleaning to base material, adherence reduces.For the stainless steel substrate that is coated with coating 2, pretreatment is also necessary.Whether this coating is for using alkaline cleaner or acetone to represent impregnable adherence do pretreatment.If pre-treatment step is out in the cold or correctly do not carry out, will affect coating adhesion.
Two coatings have all shown good stability under acid condition.Coating is at 75 ℃ 1 1/ 2hour and at room temperature to surpass 24 hours be stable.
Under alkali condition, coating 1 has shown than the better result of coating 2.Coating 1 can be born at 85 ℃ 3 hours at alkali condition, and coating 2 at 85 ℃ 2 hours.After being immersed in crude oil lower 6 months of room temperature, two coatings all show does not decompose or reduces oleophobic performance.
stage B
the coating on shell and tube exchanger surface
Coating 1 and coating 2 are applied to tube bank.All pipes pass through by the pretreatment forming as follows:
1. be immersed in (196 ℃) in liquid nitrogen
With in acid and alkaline solution place to remove dirt
3. water carrys out high-pressure wash pipe
4. pressure test is carried out in assembling tube bank
5. dismounting tube bank.Pipe is retained with dry before applying
Complete this pretreatment the previous day that is applied to pipe in coating 1 and coating 2.Therefore, this program is not followed the recommendation step of listing in stage A.When pipe has been retained when dry at ambient temperature, some pipes or wet.15 effective coatings 1 are processed, and 15 pipes of residue are processed by coating 2 by spraying.Tube Sheet of Heat Exchanger applies in both sides.Measuring final film thickness is 2-4 μ m, coating is applied to the both sides of pipe.In baking box at the scene, under the high temperature of 200 ℃ or 160 ℃, be cured/be dried 1 respectively 1/ 2hour.After completing, the heat exchanger applying is weighed, and coating layer thickness is measured.Observe some pipes and there is some coating flaws and little defect.
Then Tube Sheet of Heat Exchanger and remaining untreated pipe are fitted together.The pipe applying be placed on respectively assembling before, centre and end.Having carried out surpassing after the operation of seven months, the pipe applying is assessed.
stage C
by XPS analysis, the content of coating is measured
Afterwards by XPS (x-ray photoelectron power spectrum), also claim ESCA (chemical analysis electron spectrum) to analyze three kinds of titanium base materials that different Si oxides applies before use.XPS method provide quantitative chemical information-chemical composition with atom % represent-for surperficial outermost layer 2-10nm.
Measuring principle is that the sample to being placed in high vacuum irradiates with the X ray energy of suitable regulation, causes photoelectronic transmitting.Only from those of outermost surface layer, arrive detectors.By analyzing these photoelectronic kinetic energy, can calculate their combination energy, thereby provide them about the origin of element and electron shell.
XPS provides the quantitative data about the different chemical state (different functional groups, chemical bond, the state of oxidation etc.) of element composition and element.All elements except hydrogen and helium is detected, and the surface chemical composition of acquisition represents with atom %.
Kratos AXIS Ultra for XPS spectrum dLDthe sub-spectrometer of x ray photoelectric carries out record.Sample is analyzed with monochromatic aluminium x radiographic source.Analyzed area is at 1mm 2below.
In analysis, move wide spectrum to detect the element that is present in superficial layer.Apparent surface's composition obtains from the quantification of the concrete spectrum for each element operation.
Three samples are below carried out to XPS analysis:
1. Si oxide (new) is on titanium plate---be coated in both sides
2. Si oxide (used) is on titanium plate---be coated in a side
3. Si oxide is on DIN 1.4401 corrosion resistant plates---be coated in both sides.
Ground, a position of each sample is analyzed, except sample 1 is to analyze two positions.Result is summarised in table 2, with atom % and atomic ratio O/Si, shows apparent surface's composition.
Table 2
Sample O/Si C O Si N
1 new (position 1) 2.25 61.1 23.5 10.5 4.2
2 new (positions 2) 2.30 61.0 23.9 10.4 4.1
2 is used 2.29 68.0 19.5 8.6 3.1
3 1.46 41.9 34.3 23.4 (0.2) *
* the weak peak in concrete spectrum, signal approaches noise grade
Referring to table 2, at outermost surface, C, O and Si mainly detected, i.e. the C of 41.9-68.0 atom %, the Si of the O of 19.5-34.3 atom % and 8.6-23.4 atom %.
Note, in atomic ratio O/Si, use be the total amount of oxygen.This means the oxygen also comprising in the functional group with carbon.Otherwise, for silica, estimate theoretically a large amount of pure silicon stone SiO 2ratio O/Si should be 2.0.
the inspection of the pipe after operation
Term pollutes for being described in operating period and is formed on the deposit on pipe.Pollution is residue and the deposit being formed by crude oil, and is comprised of wax, organic moiety and mineral/inorganic part.
Visual examination shows, is coated with and specifies the pipe of coating 1 to be coated with minimum pollution in the pipe side in the face of crude oil.Equally, specify other application systems of coating 2 than exposed titanium surface, to there is the contaminant capacity of minimizing in the pipe side in the face of crude oil, but the degree reducing than coating 1 is little.
By the weight from for single pollution pipe record, deduct the average weight of clean pipe, calculate the average magnitude (table 3) of every kind of lip-deep pollution.Note, the weight of coating is not compensated, so real pollution reduction is slightly high.If estimate that coating is pure SiO 2(density 2.6g/cm 3), the amount of the coating on each pipe is about 20 grams so.
Table 3
Surface Average pollution *(g) STDEV Pollute and reduce (%)
Titanium 585 125 -
Coating 1 203 48 65
Coating 2 427 144 27
For two kinds of coat systems, the pollution of pipe is more easily removed than being bonded at the lip-deep pollution of exposed titanium, in Table 4.By with the manual wiping pipe of fabric with clean to test the difference in requirement for cleaning with water under high pressure.Only with fabric wiping pipe, show to pollute to be very easy to remove from applying pipe, contrary with uncoated pipe.By water is sprayed, remove on the surface that all pollutions except the little patch in a place or two places can both apply from coating 1.On the surface applying in coating 2, after water injection is clean, also there is more pollution.This pollution has the outward appearance of slight combustion oil.
At contact point, observe some coating losses, but the coating surface of contact crude oil is in shape on the whole.
In the face of on the side of seawater, two kinds of coatings are variation and can be easy to peel off all.
Table 4
For removing packing ring, the tolerance that coating is immersed in liquid nitrogen detects.The pipe of a coating 1 and a coating 2 is processed at-196 ℃ in liquid nitrogen, to remove rubber washer.There is not being subject to the change of extreme temperature in coating.With water under high pressure, pipe is cleaned subsequently, it has removed nearly all pollution.For arbitrary coat system, all do not observe coating boundary or inefficacy.

Claims (4)

1. a shell and tube exchanger (1), comprise housing (2), it has the import end cap (3) of the first end (4) that is attached to described housing (2), wherein export the second end (6) that end cap (5) is attached to described housing (2), tube bank (7) is contained in described housing (2), described tube bank (7) comprises the pipe (8) of a plurality of parallel interval, its first end from described tube bank (9) traverses the inside of housing (2) to the second end (10), and wherein a plurality of baffle plates (11) are arranged in described housing (2), thereby support the pipe (8) of the described parallel interval of described tube bank (7), it is characterized in that:
Described shell and tube exchanger has the Si oxide of comprising SiO xcoating, it has the atomic ratio of O/Si > 1, carbon content>=10 atom %, and the about coating layer thickness of 1-30 μ m, described coating is made and is applied at least a portion on described shell and tube exchanger surface by sol-gel process.
2. shell and tube exchanger according to claim 1, is characterized in that, at the bed thickness of described lip-deep described coating, is 1.5-25 μ m, preferably 2-20 μ m, more preferably 2-15 μ m, even more preferably 2-10 μ m, most preferably 3-10 μ m.
3. according to the shell and tube exchanger described in any one in claim 1 or 2, it is characterized in that, comprise Si oxide SiO xdescribed coating there is O/Si>=1.5-3, the atomic ratio of O/Si>=2-2.5 preferably.
4. according to the shell and tube exchanger described in any one in claim 1-3, it is characterized in that, described composition has carbon content >=20-60 atom %, preferably >=30-40 atom %.
CN201280058344.7A 2011-11-28 2012-11-28 Shell and tube heat exchanger with improved anti-fouling properties Pending CN104067082A (en)

Applications Claiming Priority (3)

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SE1151125 2011-11-28
SE1151125-0 2011-11-28
PCT/SE2012/051309 WO2013081536A1 (en) 2011-11-28 2012-11-28 Shell and tube heat exchanger with improved anti-fouling properties

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US (1) US20140338867A1 (en)
EP (1) EP2786085A1 (en)
KR (1) KR20140106604A (en)
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CA (1) CA2857248A1 (en)
WO (1) WO2013081536A1 (en)

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DE102009024320A1 (en) * 2009-06-03 2010-12-09 Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. Coating comprises corroded nanoparticular metal-/silicon oxide layers, in whose surface, fluorine compounds are bounded, or silica, silicon oxide compound, alumina and/or titania or mixed oxides of titania/silica

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020506298A (en) * 2017-01-18 2020-02-27 プラストコル−インターナツィオナール エスアーＰｌａｓｔｏｃｏｒ‐ｉｎｔｅｒｎａｔｉｏｎａｌ ＳＡ Use of SiO2 coating in water transport cooling system

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WO2013081536A1 (en) 2013-06-06

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