EP2188061A2 - Cuve a paroi composite comprenant une couche organique - Google Patents
Cuve a paroi composite comprenant une couche organiqueInfo
- Publication number
- EP2188061A2 EP2188061A2 EP08837869A EP08837869A EP2188061A2 EP 2188061 A2 EP2188061 A2 EP 2188061A2 EP 08837869 A EP08837869 A EP 08837869A EP 08837869 A EP08837869 A EP 08837869A EP 2188061 A2 EP2188061 A2 EP 2188061A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- tank
- polymeric
- shell
- polymeric compound
- 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.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
- B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/148—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using epoxy-polyolefin systems in mono- or multilayers
Definitions
- the present invention belongs to the field of equipment intended to contain potentially corrosive fluids, especially intended for the production of hot water.
- It relates to a vessel whose wall is made from a composite material comprising three associated layers, which provides both the rigidity due to a high adhesion of the wall and its physical and chemical stability vis-à-vis a corrosive fluid or can be in certain conditions of use.
- Another object of the invention is a method of manufacturing such a composite wall.
- the balloons used to supply hot water to individual or collective equipment are generally made from a steel shell, covered with a thermal insulating material.
- the internal surface must be treated to resist corrosion as the domestic hot water contains impurities and aggressive treatment products with respect to the steel, especially as the temperature is maintained at a high level to be distributed at 65 ° C. Not only does the installation deteriorate, which is a problem in itself, but also corrosion promotes biofouling by bacterial growth on the inner wall. It is obvious that the production of hot water, intended especially for food use, can not be subject to this kind of hazard.
- a protective material on the inner surface of the steel shell in contact with the liquid.
- the deposited material must be chosen so that its coefficient of expansion is close to that of the steel so that the protective layer remains integral with the steel shell during temperature variations of the system. It is for example known to project a molten metal material on the shell whose surface has previously been roughened. This technique also called "metallization" because of the contribution of material is carried out in the form of fine vaporized and cooled metal droplets, is commonly implemented with aluminum, which offers in addition the advantage of a cathodic protection of steel.
- the solution provided by the present invention is to coat the inner face of the tanks with a corrosion-resistant material, such as a plastic material.
- a corrosion-resistant material such as a plastic material.
- the walls of the tanks are commonly made of steel, a material that provides the rigidity and the necessary mechanical strength at a moderate cost price.
- steel does not have a particular affinity for plastics, and on the other hand, it has a significant coefficient of expansion in the range of temperatures concerned, ranging from -2O 0 C to 100 0 C during various handling, storage, transport and operation, while plastics have a very different coefficient of expansion.
- the expansion can cause deviations of several millimeters, leading to the dissociation of the coating and the deterioration of the wall. It is therefore imperative to ensure a strong cohesion of the coating with the wall.
- thermoplastic polymeric compounds can be used as an anticorrosive inner lining of tanks, when applied to a metallized steel shell, i.e., the inner face of the shell has been spray-treated. a molten metal material, which has the effect of rendering the surface porous.
- the coating technique used is inspired by well-known rotational molding techniques and brings an unexpected result. Indeed, the thermoplastic properties of many polymers are known and used to make all kinds of objects, by different molding techniques, and among them rotomolding. This method of transformation of plastics is carried out in three steps: filling of a mold with a thermoplastic polymer in the form of granules or powder, melting of the plastic material, then solidification.
- An object of the present invention is therefore to provide a tank useful for receiving corrosive liquids, for example for the production of hot water, the wall of which, while retaining its previous mechanical properties, is insensitive to chemical attack and more particularly to oxidation and chlorine, without resorting to a metallization step.
- Another object of the invention is to provide a vessel whose wall is resistant to stress due to thermal expansion.
- Another object of the present invention is to provide a tank meeting the above requirements for periods of several years, and with a moderate manufacturing cost.
- Another object of the invention is to provide a method of manufacturing said tanks which is reliable and easy to implement.
- the present invention makes it possible to offer establishments such as hotels or hospital centers a means of distributing hot water in complete safety, without significant additional cost of equipment or operation.
- the subject of the present invention is a vessel intended to contain a corrosive fluid, original in that it has a composite wall comprising an outer steel shell, an organic intermediate layer, and an inner layer based on a compound thermoplastic polymer modified with 10% to 50% of a diacid.
- the outer shell is the element ensuring the mechanical strength of the composite wall. It gives its shape to the tank and also serves as a support for other layers. It is commonly made of steel. It is possible to use, for example, non-alloyed hot-rolled structural steels that meet the standards in force. Its thickness is chosen according to the operating pressure and the diameter of the tank, in accordance with the pressure vessel code and / or the regulations in force in the country of use. It can thus be between 2 mm and 15 mm, more frequently between 4 mm and 8 mm. Manufacturers of heating equipment are familiar with these standards and the qualities of steel to be implemented.
- the surface of the part to be coated is previously prepared to remove oxides and calamines, increase its roughness and allow particles to anchor in the irregularities of the surface .
- the method called impact treatment can be used. It consists in projecting a natural or artificial abrasive onto the surface to be treated. The projection can be done by compressed air, either by a vacuum system (suction, suction, Giffard effect), or by a direct pressure system (overpressure). Depending on the size of the abrasive particles we are talking about sanding (fine particles) or shot blasting (larger particles).
- the depth of the roughness profile is between 5% and 25% of the thickness of the subsequent coating, with an optimum value around 25% which has the effect of increasing the contact area by a factor of 3 or 4.
- the inner face of the steel shell advantageously has a roughness Ra corresponding to the mean arithmetic mean deviation from the mean line of the surface, between 10 ⁇ m and 150 ⁇ m, preferably from 10 ⁇ m to 150 ⁇ m. about 15 ⁇ m. It is completely covered by the intermediate layer which adheres to it by a mechanical phenomenon with a force which can vary from 20 to 115 MPa after sanding, according to the processes and the materials.
- the intermediate layer of the wall according to the invention is an organic compound layer. It may consist of an epoxy, ie a resin with thermosetting properties well known to those skilled in the art. It can be obtained by one of the thermal treatment techniques with material input available to those skilled in the art. For example, it is possible to use an electric discharge of an electrode (Corona effect) or by friction (triboelectric effect). In this case, a substrate (here the steel shell) is preheated. The reactive chemical species (epoxy or other resin to be added) are then adsorbed on the surface, dissociate and diffuse in the matrix of the solid or liquid phase substrate, or accumulate and lead to the formation of a layer of epoxy.
- an epoxy ie a resin with thermosetting properties well known to those skilled in the art. It can be obtained by one of the thermal treatment techniques with material input available to those skilled in the art. For example, it is possible to use an electric discharge of an electrode (Corona effect) or by friction (triboelectric effect). In this case, a substrate (here the steel
- the wall of the vessel may further comprise an underlayer hooking between the steel shell and the intermediate layer. Indeed, in some cases, the roughness of the hull must be reinforced.
- the wall of the tank according to the present invention comprises a third layer, the innermost, intended to be in contact with a corrosive fluid and thus to protect the outermost layers of chemical attack.
- a thermoplastic polymer that is to say softenable by heating and hardening by cooling without chemical reaction.
- compounds used in industry can be obtained in various forms, for example in the form of powders or granules, which can be conveniently used in plastics processes.
- additives or technological aids such as a load up to 40% by weight (talc or calcium carbonate for example), reinforcing additives, for example fiberglass or mica at 20 to 30% by weight.
- said polymeric compound comprises polar groups of electronegative character. It has indeed been observed that the choice of such polymers leads to an even stronger cohesion between the inner layer and the intermediate layer. These groups may be originally present in the chosen polymer or provided by a suitable chemical reaction, for example by functional grafting or by chemical modification of the polymer.
- the polymeric compound used for the inner layer according to the invention may for example be selected from ethylene polymers, propylene polymers, fluorocarbon resins, polyoxymethylenes.
- Polyethylenes can be employed from among many existing types, for example from low density polyethylenes (or LDPE) having a density of between 0.92 g / cm 3 and 0.94 g / cm 3 , or from polyethylenes. high density (HDPE), having a density of between 0.95 g / cm 3 and 0.97 g / cm 3 . It is also possible to use polypropylenes, those used in the industry being almost always isotactic. They are often associated with a copolymer.
- the fluorocarbon resins of formula [-CH 2 -CF 2 -] n are also usable for producing the inner layer of the tank according to the invention.
- the main fluorocarbon resins are PTFE (polytetrafluoroethylene), FEP (fluorinated ethylene-propylene), PFA (perfluoroalkoxy), PVDF (polyfluorovinylidene), ETFE (modified copolymer of ethylene and tetrafluoroethylene) and ECTFE (ethylene / chlorotrifluoroethylene).
- POM polyoxymethylene
- They are technical thermoplastics which are distinguished by a high tensile strength, even at temperatures of -40 ° C, a Young's modulus of the order of 2800 to 3600 MPa, a very good dimensional stability when hot.
- polystyrene polypropylenes grafted with acrylic acid, maleic anhydride or styrene, polypropylenes crosslinked with silanes can be used which are thus functionalized as required.
- This list is not exhaustive and concerns all thermoplastics, including graft thermoplastic sub-families.
- the polymeric compound is a diacid modified polymer.
- the polymeric compound may be a polypropylene modified with maleic anhydride.
- the insertion rate of the anhydride unit may be higher or lower.
- the polymeric compound is a polypropylene modified with 10% to 50% maleic anhydride, in mole.
- the polymeric compound is a polypropylene modified with 20% maleic anhydride, in mole.
- the intermediate layer must have a thickness of between a few microns and 1 mm. According to the preferred embodiment of the present invention, its thickness is about 200 microns.
- the tank according to the invention intended to contain a corrosive fluid has a composite wall comprising an outer steel shell, an intermediate epoxy resin layer and a maleic anhydride modified polypropylene inner layer.
- the tank according to the invention can be manufactured by any known method allowing the deposition of organic layers on the one hand and polymeric on the other hand.
- a particularly suitable method has been developed for producing the composite wall as described above. In principle, it consists in carrying out the organic deposition by the techniques commonly used for the manufacture of conventional tanks, then in coating this surface with an original process.
- a method of manufacturing a vessel for containing a corrosive fluid said vessel having a composite wall comprising an outer shell of steel, an organic intermediate layer and an inner layer based on a thermoplastic polymeric compound, method which comprises the following steps: i) - a prior step of applying the intrinsic organic layer to the applied materials, to form said intermediate layer deposited on the steel shell, and ii) - a coating step consisting in: - introducing a powdered polymeric compound, modified by 10% to 50% of a diacid, into the steel shell covered with the organic layer attached to a biaxial rotation system,
- the process according to the invention may comprise mixing the organic layer and the polymeric compound in the form of a powder or a solution, during a prior stage before being applied in the steel hull.
- the deposition of the intermediate layer on the steel shell can be achieved by a technique known per se.
- the technique of electropowdering will be used for the application of an organic layer consisting of an epoxy compound in powder form.
- the organic layer consists of an epoxy compound in liquid form
- it will be applied by the most common techniques such as for example projection by means of a bi-component or single-component spray gun.
- the steel shell before the application step, may be subjected to an impact treatment to increase its roughness.
- This treatment consists in projecting a natural or artificial abrasive onto the surface to be treated.
- the conditions of implementation are easily chosen by those skilled in the art who already practice these techniques of sanding (fine particles) or shot blasting (larger particles).
- an attachment sub-layer is applied to the shell. It can be carried out according to the same process as that used for the deposition of the intermediate layer, with different materials.
- the third layer can be applied. This is to reproduce the inner shape of a cavity (the inner surface of the wall of the tank) which can range from one to 100,000 liters.
- a cavity the inner surface of the wall of the tank
- one proceeds in three phases, by analogy with discontinuous processes of plastics processing: filling the cavity, melting of the polymeric material, solidification of the polymeric material.
- a first step after a possible preheating, the cavity is loaded with powder of polymer material, whose weight corresponds to that of the coating to be obtained.
- the tank is then closed and is rotated by a mechanical system that allows it to rotate about two axes oriented differently, generally perpendicular to each other.
- the tank rotating in all directions, is then heated up to the temperature of good melting, the melting point of the thermoplastic polymers being generally between 150 0 C and 300 0 C.
- the powder of molten plastic material flows by gravity on the walls.
- the rotational speeds being low the effect of the centrifugal force is negligible.
- the melting of the powdered polymeric compound is obtained by heating the metallized shell containing it by an external heating means.
- the heat input is achieved by means of an oven, a gas ramp or infrared panels.
- the heated tank transmits its heat to the powder whose grains melt and stick on the wall.
- the thermoplastic whose temperature is above its melting point has a viscous consistency.
- the device is removed from the oven and allowed to cool. Cooling can be accelerated by projecting fresh air and / or water mist onto the tank.
- thermoplastic polymers can be used in the process as just described.
- the polymers employed in the process according to the invention are chosen from those which are used in the wall of the tank described above.
- a particularly advantageous embodiment of the process according to the invention uses a powdered polymeric compound comprising polar groups of electronegative character.
- the polymeric powder compound used in the process according to the invention may be chosen from ethylene polymers, propylene polymers, fluorocarbon resins, polyoxymethylenes.
- said polymeric powder compound is a diacid modified polymer. More preferably, said polymeric powder compound is a polypropylene modified with maleic anhydride.
- the tank as described and claimed in the present application may be manufactured by the method of the invention or by any other suitable method. It finds application in various industrial fields, such as the production of hot water, but also the industrial production of chemical or biological substances in reactors, or the road or rail transport of corrosive fluids.
- the fluids used in these applications may be at low, medium to high temperatures and may be more or less aggressive.
- the characteristics of the tank allow its use in all conditions without long term degradation.
- another object of the present invention is a device for storing, transporting, storing or producing a corrosive fluid, comprising a composite wall vessel. comprising an organic layer as described above. More particularly, is claimed a hot water production device comprising a composite wall vessel according to the invention.
- This wall was made from a steel shell of unalloyed construction, complying with the European standard bearing the N 0 EN 10025: 1993 (symbolic designation: S235JR, numerical designation: 1.0037) and with the French standard N 0 NF A 35-501 (designation: E 24-2), of thickness 3 mm, and forming a cylindrical tank with a volume of 50 liters.
- the inner side has undergone impact treatment using a sandblaster equipped with a cylindrical nozzle projecting corundum with an air pressure of about 7 bars.
- the projection angle is practically tangential with respect to the surface (30 to 40 degrees).
- the ambient temperature is at 20 ° C. in order to avoid oxidation as much as possible.
- the inner face of the steel shell has a Ra roughness of 15 microns, which represents 25% of the thickness of the intermediate layer which will now be deposited.
- the intermediate layer is epoxy resin. It is deposited by electropowdering.
- the spray gun used is automatically regulated.
- the static charge is produced by the electric discharge of an electrode (corona effect).
- the part to be applied is connected to a mass.
- the tank is preheated to 150 ° C. in order to increase the epoxy thickness.
- the operation is carried out in manual mode through the inspection hatch inside the tank. Once the thickness of 200 microns deposited, the room is maintained at a temperature of 190 ° C for 14 min. Then the tank is cooled in the open air to room temperature.
- the inner layer of the wall consists of a polypropylene modified with maleic anhydride.
- the degree of insertion of the anhydride unit is 20 mol%.
- Such a polypropylene modified with maleic anhydride is obtained by the known processes for manufacturing the polymeric raw materials. It was done in the following way.
- the tank is mounted on a mechanical system that allows it to rotate about two perpendicular axes. The whole is introduced into an oven and is preheated to 22O 0 C for 20 minutes. Then 1.4 kg of modified polypropylene powder is introduced into the cavity of the tank and the tank is closed by quick couplings. It is set in motion and is maintained at a temperature of 220 ° C for 14 minutes.
- the polymeric layer thus obtained has a constant thickness of about 120 microns over the entire internal surface of the vessel.
- the composite wall has been subjected to various tests to evaluate its performance. It has been found on the one hand that during temperature variations, the layers remain united even though their coefficient of expansion is different. This result is assumed to be due to the fact that the intermediate layer absorbs the differential expansion between the materials of the outer and inner layers of the wall.
- the tearing tests were carried out using a traction machine specially designed for this purpose (shown in FIG. 1) on specimens prepared with the materials described in Example 1 and under similar conditions.
- Each test piece 1 consists of a steel plate covered with the organic epoxy layer 2, covered with a layer 3 of polypropylene modified by melting in a furnace.
- the bottom plate 2 has a dimension of 200 mm ⁇ 100 mm, it is furthermore provided with means for suspending masses, by example of rings 6, while the Top plate 4 has a surface area of only 50 mm x 50 mm. Their thickness is about 3 mm, as well as that of the polymeric layer.
- the layer 3 of polymer is cut in its thickness around the upper plate 4, so as to laterally isolate a polymer coating sample 7 of 50 mm side centered on the axis of the hook 5. suspends the test piece 1 by the hook 5 and attaches loads to the rings 6, of increasing mass (10 kg in 10 kg). Thus measures the mass required to peel the sample at least 7 of a plate 2 or 4, in less than a minute and the corresponding force is calculated, expressed as daNcm "2.
- one material is considered to be integral with another when the tearing force necessary to separate them is greater than 0.8 MPa, ie 8 daNcm -2 .
- 0.8 MPa ie 8 daNcm -2
- the composite wall of the specimens E1 to E5 has a very strong cohesion.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0705488A FR2919279B1 (fr) | 2007-07-26 | 2007-07-26 | Cuve a paroi composite comprenant une couche organique. |
PCT/FR2008/001114 WO2009047407A2 (fr) | 2007-07-26 | 2008-07-25 | Cuve a paroi composite comprenant une couche organique |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2188061A2 true EP2188061A2 (fr) | 2010-05-26 |
Family
ID=39226818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08837869A Withdrawn EP2188061A2 (fr) | 2007-07-26 | 2008-07-25 | Cuve a paroi composite comprenant une couche organique |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2188061A2 (fr) |
FR (1) | FR2919279B1 (fr) |
WO (1) | WO2009047407A2 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012092104A1 (fr) | 2010-12-30 | 2012-07-05 | Ticona Llc | Poudre contenant un polymère de polyoxyméthylène pour revêtir des substrats métalliques |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3207358A (en) * | 1961-07-27 | 1965-09-21 | Gen Electric | Water storage tanks and methods of making the same |
JPS534880B2 (fr) * | 1973-11-22 | 1978-02-21 | ||
US5474846A (en) * | 1993-01-26 | 1995-12-12 | Haldenby; George A. | Uniform polymeric coated interior cylinder surface |
US20030068434A1 (en) * | 2001-08-21 | 2003-04-10 | Moore James B. | Method for bonding thermoplastic films to metal surfaces of cylinders, vessels and component parts |
-
2007
- 2007-07-26 FR FR0705488A patent/FR2919279B1/fr not_active Expired - Fee Related
-
2008
- 2008-07-25 WO PCT/FR2008/001114 patent/WO2009047407A2/fr active Application Filing
- 2008-07-25 EP EP08837869A patent/EP2188061A2/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2009047407A3 * |
Also Published As
Publication number | Publication date |
---|---|
WO2009047407A2 (fr) | 2009-04-16 |
WO2009047407A3 (fr) | 2009-06-11 |
FR2919279A1 (fr) | 2009-01-30 |
FR2919279B1 (fr) | 2012-09-07 |
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