WO2000079199A1 - Echangeurs thermiques formes de tubes lies thermiquement - Google Patents

Echangeurs thermiques formes de tubes lies thermiquement Download PDF

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Publication number
WO2000079199A1
WO2000079199A1 PCT/CA2000/000742 CA0000742W WO0079199A1 WO 2000079199 A1 WO2000079199 A1 WO 2000079199A1 CA 0000742 W CA0000742 W CA 0000742W WO 0079199 A1 WO0079199 A1 WO 0079199A1
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WO
WIPO (PCT)
Prior art keywords
tubes
weight
heat exchanger
lcp
itp
Prior art date
Application number
PCT/CA2000/000742
Other languages
English (en)
Inventor
Kenneth Earl Stevens
Original Assignee
Dupont Canada Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dupont Canada Inc. filed Critical Dupont Canada Inc.
Publication of WO2000079199A1 publication Critical patent/WO2000079199A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73115—Melting point
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/52—Joining tubular articles, bars or profiled elements
    • B29C66/522—Joining tubular articles
    • B29C66/5227—Joining tubular articles for forming multi-tubular articles by longitudinally joining elementary tubular articles wall-to-wall (e.g. joining the wall of a first tubular article to the wall of a second tubular article) or for forming multilayer tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • B29C66/7234—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a barrier layer
    • B29C66/72343—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a barrier layer for liquids
    • 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
    • F28D7/0041—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 for only one medium being tubes having parts touching each other or tubes assembled in panel form
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/06—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material
    • F28F21/062—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material the heat-exchange apparatus employing tubular conduits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/10—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using hot gases (e.g. combustion gases) or flames coming in contact with at least one of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91411—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the parts to be joined, e.g. the joining process taking the temperature of the parts to be joined into account
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91933—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined higher than said fusion temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/18—Heat-exchangers or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/60—Multitubular or multicompartmented articles, e.g. honeycomb
    • B29L2031/601—Multi-tubular articles, i.e. composed of a plurality of tubes
    • B29L2031/602—Multi-tubular articles, i.e. composed of a plurality of tubes composed of several elementary tubular elements

Definitions

  • Efficient plate type units (panels) used in nylon heat exchangers are produced by a twin sheet thermoforming process with internal gas assist, which gives an essentially flat plate consisting of a number of tubes joined by ligatures formed from the sheets of nylon. This process is described in US 5,195,240.
  • Such plates and the heat exchangers formed from them provide excellent heat transfer efficiency for the space volume occupied, but can tolerate only relatively low internal pressures, restricting their applicability.
  • Tubing formed by extrusion can tolerate much higher internal pressure.
  • a high efficiency exchanger a large number of small tubes are required; constraint and support of these tubes is required.
  • Use of tubing located between two bonded sheets of plastic to achieve this support is described in US 5,469,915. However, this still requires ligatures between the tubes, which reduces heat transfer efficiency.
  • the present invention provides A heat exchanger made from polymeric tubes in the form of tube sheets with a multiplicity of at least three tubes adjacent each other in a plane, bonded together by an outer layer on the tubes which is melted together.
  • Fig. 1 is a schematic representation of a tube sheet of the invention, prior to melt bonding.
  • Fig. 2 is a schematic view of a tube of the invention with outer and inner layers.
  • Panel formation from these tubes is accomplished by heating a bundle of tubes constrained in intimate contact in a parallel, essentially flat manner such that bonding between the tubes occurs. This can be accomplished for example, by heating with hot air or an oven, such that the surface temperature of the tubes reaches about 200°C to effect tube to tube bonding.
  • Fig. 1 shows tubes 11 - 16 of the invention laid adjacent to each other to form a tube sheet 10, with interstices at 18 - 20 and with holes 17 in the tubes.
  • Fig. 2 shows an enlarged view of a tube 11 used in the invention, with an outer layer 21, an inner layer 22 and a hole 17.
  • the tubes can be made form a variety of materials, including a polyamide modified to be thermally bondable or heat-sealable, eliminating the need for phenol.
  • These films can be produced by coextrusion of a thin bondable layer (0.013-0.076 mm) preferably of a blend of polycaprolactam (19-40% by weight) polymer prepared from equimolar amounts of 2-methylpentamethylene diamine and 1,12-dodecanedioic acid (20-40% by weight) such as "D-12" high performance nylon sold by DuPont, a copolymer of ethylene and a vinyl carboxylic acid, partially neutralized by a Group 1A,2A or 3 A metal ion (15-58% by weight) such as "Suriyn" ionomer sold by DuPont, and a polymeric grafting agent (3-16% by weight) such as "EBAGMA” grafting agent sold by DuPont, optionally containing heat stabilizers, pigments and other know adjuvants, onto
  • the polyamide-based composition of the inner layer of each sheet is a heat formable laminating film made from a multi-phase thermoplastic resin composition comprising the following main components:
  • At least one polyamide resin selected from aliphatic and semi-aromatic polyamides that can be either semi-crystalline or amorphous in structure having a number average molecular weight of at least about 5000;
  • At least one polyamide resin comprising at least one pendant alkyl branch having 1 to 3 carbon atoms within at least two amide linkages along the polymer backbone and at least one sequence of at least seven consecutive carbon atoms, excluding carbon atoms in pendant alkyl branches, if any, within at least two amide linkages along the polymer backbone, the melting point of the polyamide being less than 200°C;
  • E is ethylene and is at least 50 % by weight of E/X/Y
  • X is from 1-35 % by weight of an acid containing unsaturated mono-carboxylic acid
  • Y is 0-49 % by weight of a moiety derived from at least one alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof where the alkyl groups contain 1-12 carbon atoms, and further wherein the acid groups in the acid-containing moiety are neutralized from 0-100% by weight of a metal ion;
  • At least one polymeric grafting agent which contains reactive groups selected from at least one of epoxides, isocyanates, aziridines, silanes, alkyl halides, alpha-halo ketones and aldehydes, or oxazoline, which reacts with the acid- contairiing moieties in component iii) and additionally reacts with the graft sites of components i) and ii), and the weight percent of the monomer(s) containing the reactive groups is 0.5-15 weight percent of the polymeric grafting agent, and the remainder of the polymeric grafting agent contains at least 50 % by weight of ethylene and from 0-49 % by weight of a moiety derived from at least one alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof where the alkyl groups contain 1-12 carbon atoms.
  • component i) and ii) equals from about 29 to about 72% by weight.
  • Polymers that may be used in the tubes include nylon 66, nylon 6, blends of nylon 6 and nylon 66, and other materials, including: from about 1 to about 40 % by weight of (ii) at least one polyamide resin comprising at least one pendant alkyl branch having 1 to 3 carbon atoms within at least two amide linkages along the polymer backbone and at least one sequence of at least seven consecutive carbon atoms, excluding carbon atoms in pendant alkyl branches, if any, within at least two amide linkages along the polymer backbone, the melting point of the polyamide being less than 200°C; the polyamides of I) and ii) having graft sites and forming the continuous phase of the composition; and with the proviso that the sum of components i) and ii) is from about 29 to about 72% by weight;
  • E is ethylene and is at least 50 % by weight of E/X/Y
  • X is from 1-35 % by weight of an unsaturated mono-carboxylic acid
  • Y is 0- 49 % by weight of a moiety derived from at least one alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof where the alkyl groups contain 1-12 carbon atoms, and further wherein the acid groups in the acid-containing moiety are neutralized from 0-100% by weight of a metal ion; and
  • At least one polymeric grafting agent which contains reactive groups selected from at least one of epoxides, isocyanates, aziridines, silanes, alkyl halides, alpha-halo ketones and aldehydes, or oxazoline, which grafting agents react with the acid-containing moieties in component iii) and additionally react with the graft sites of components i) and ii), and the weight percent of the monomer(s) containing the reactive groups is 0.5-15 weight percent of the polymeric grafting agent, and the remainder of the polymeric grafting agent contains at least 50 % by weight of ethylene and from 0- 49 % by weight of a moiety derived from at least one alkyl acrylate, alkyl methacrylate, alkyl vinyl ether, carbon monoxide, sulfur dioxide, or mixtures thereof where the alkyl groups contain 1-12 carbon atoms.
  • the end group balance of the low temperature nylon has been found to affect the processing and properties of the final film product.
  • high performance nylon, specifically D12, with balanced or carboxyl rich end groups in the formulation reduces filter pressure drops and melt viscosities during film production, and improves film dimensional stability during heating - compared to the incorporation of D12 having amine-rich ends.
  • a preferred form of the present formulation comprises from about 17 to about 54% by weight, more preferably, from about 18 to about 47% by weight, and most preferably, from about 19 to about 40% by weight of Nylon 6 (component i); from about 1 to about 40% by weight, more preferably about 10 to about 40% by weight; most preferably from about 20 to about 40% by weight of Nylon D12 (low temperature nylon), (component ii); from about 5 to about 69%, more preferably from about 11 to about 58% by weight, and most preferably from about 15 to about 48% by weight of ethylene E/X/Y (component iii); from about 0.5 to about 45% by weight, more preferably from about 2 to about 28%, most preferably from about 3 to about 16% by weight of EBAGMA (component iv); with the total amount of nylon ranging preferably from about 29 to about 72% by weight, more preferably from about 38 to about 71% by weight, and most preferably from about 45 to about 70% by weight. It should be noted that for the ranges
  • the formulation comprises from about 55 to about 80% by weight of components (i) and (ii), with the nylon components I) and ii) taken together always in the majority (the iii) component which can be "SURLYN” ionomer produced by DuPont, and the iv) coponent which can be "EBAGMA” comaptibilizer produced by DuPont, are in the minority), but component (i) may range from about 20 to about 60% by weight, and component (ii) may range from about 10 to about 35% by weight.
  • the formulations disclosed herein may include antioxidants, heat stabilizers or mixtures thereof. Typically these comprise from about 0.05 to about 5.0% by weight, preferably from about 0.05 to about 2.0% by weight.
  • Organic heat stabilizers have been found to be better than the metal halide heat stabilizers, such as CuI/KI, in terms of retention of film physical properties after oven aging for one hour at 200°C.
  • "Irganox" 1010/1098 blend of two hindered phenolic antioxidants produced by Ciba Specialty Chemicals is a preferred example of such a material. This substance also reduces filter pluggage and reduces pressure during the production of the film.
  • Other optional ingredients may be selected from flame retardants, antiblocking agents, slip additives, pigments or dyes, processing aids, plasticizers and ultra-violet blocking agents. These may be used in suitable quantities as are well known to those skilled in the art.
  • Liquid crystal polymers can also be used in forming layers in the tubes, including:
  • One of the materials which is part of the HESM is an isotropic thermoplastic (FTP).
  • Isotropic herein means that the polymer is isotropic when tested by the TOT Test described in U.S. Patent 4,118,372, which is hereby included by reference. Any ITP may be used so long as it meets certain requirements. It must of course withstand the temperatures to which the HESM is exposed, and should throughout that temperature range provide sufficient strength (together with the LCP) to the HESM to reasonably maintain its shape and contain the fluids in the heat exchanger, as needed. If it is exposed to one or more of the fluids in the heat exchanger (or any other adventitious materials that may contact it) it should be preferably reasonably chemically stable to those fluids so as to maintain its integrity.
  • ITPs sometimes have serious drawbacks when the are the only materials in HESMs.
  • an ⁇ TP may not be chemically stable to one or more of the fluids in the heat exchanger, for instance, many polyesters hydrolyze or otherwise degrade in the presence of water, water-alcohol, or water-glycol mixtures, especially at higher than ambient temperatures.
  • Many ITPs are relatively permeable to many liquids and/or gases, and therefore allow losses and/or migration of these materials in or from the heat exchanger.
  • Some ITPs may be swollen by one or more of the fluids used in the heat exchanger thereby changing their dimensions and/or physical properties. All of the above are of course problems in plastic heat exchangers.
  • thermotropic liquid crystalline polymer used in the HESM often alleviates or eliminates one or more of the above mentioned problems.
  • LCP thermotropic liquid crystalline polymer
  • an LCP is meant a polymer that is anisotropic when tested in the TOT Test described in U.S. Patent 4,118,372. If the LCP layer is placed between a fluid and any particular ITP in the HESM it usually protects that ITP from chemical degradation by the fluid, and/or also often protects the ITP from being swollen by that fluid. In addition, even if the ITP is swollen, the LCP because of its high relative stiffness, and the fact that it is not swollen by many fluids, help the overall HESM maintain its shape and dimensions.
  • the LCP acts as an excellent barrier layer to many fluids.
  • the commonly used internal coolant is a mixture of a glycol and water
  • the external coolant is air.
  • ITPs diffusion of water and/or glycol is so rapid that frequent replenishment of the water/glycol mixture is needed. If an LCP layer is included, the diffusion is greatly decreased.
  • the LCP is usually the more expensive of the polymers present in the HESM, it is economically preferable to limit its use. Therefore, in most constructions it is preferred that the LCP is present in relatively thin layer(s) and that layer(s) of the ITP be relatively thick so as to carry much of the structural load of the HESM (i.e., pressure of the fluid(s), maintain structural shape and dimensions, etc.).
  • the HESM is made up of one or more LCP layers and one or more layers of ITP. If more than one layer of LCP or ITP is present, more than one type of LCP or ITP, respectively, can be used. In addition other layers may be present. For example, so called tie layers, also called adhesive layers, may be used to increase the adhesion between various LCP and ITP layers, or between ITP layers or between LCP layers.
  • tie layers also called adhesive layers, may be used to increase the adhesion between various LCP and ITP layers, or between ITP layers or between LCP layers.
  • the number and placement of the various layers in the HESM will vary depending on the particular polymers chosen, the fluids used in or by the heat exchanger, temperature requirements, environmental needs, etc.
  • Fluids 1 and 2 represent the fluids involved in the heat transfer:
  • tie layers may be present between all, some or none of the various polymer layers.
  • constructions may be particularly useful in certain situations. If Fluid 1 but not Fluid 2 chemically attacked the ITP, construction (a) may be particularly useful, but (c) and (f) may also be utilized. If both Fluids 1 and 2 attacked the ITP present construction (c) or (f) may be particularly useful. If one wanted to minimize diffusion of one fluid to another, a construction having two LCP layers, such as (c), (d) or (f) could be chosen. If a special surface is required to reduce abrasive damage on the Fluid 1 side, but great stiffness is also required from the ITP, a construction such as (e) could be chosen wherein ITP-1 and ITP-2 have the requisite properties. These and other combinations of layers having the correct properties for various applications will be obvious to the artisan.
  • Useful LCPs include those described in U.S. Patents 3,991,013, 3,991,014 4,011,199, 4,048,148, 4,075,262, 4,083,829, 4,118,372, 4,122,070, 4,130,545, 4,153,779, 4,159,365, 4,161,470, 4,169,933, 4,184,996, 4,189,549, 4,219,461, 4,232,143, 4,232,144, 4,245,082, 4,256,624, 4,269,965, 4,272,625, 4,370,466, 4,383,105, 4,447,592, 4,522,974, 4,617,369, 4,664,972, 4,684,712, 4,727,129, 4,727,131, 4,728,714, 4,749,769, 4,762,907, 4,778,927, 4,816,555, 4,849,499, 4,851,496, 4,851,497, 4,857,626, 4,864,013, 4,868,278, 4,882,410, 4,923,94
  • thermotropic LCPs include polyesters, poly(ester-amides), poly(ester-imides), and polyazomethines.
  • LCPs that are polyesters or poly( ester-amides). It is also preferred in these polyesters or poly(ester-amides) that at least about 50 percent, more preferably at least about 75 percent, of the bonds to ester or amide groups, i.e., the free bonds of -C(O)O- and -C(O)NR 1 - wherein R 1 is hydrogen or hydrocarbyl, be to carbon atoms which are part of aromatic rings.
  • Included within the definition herein of an LCP is a blend of 2 or more LCPs or a blend of an LCP with one or more ITPs wherein the LCP is the continuous phase.
  • Useful ITPs are those that have the requisite properties as described above, and include: polyolefins such as polyethylene and polypropylene; polyesters such as poly( ethylene terephthalate, poly(butylene terephthalate), poly(ethylene 2,6- napthalate), and a polyester from 2,2-bis(4-hydroxyphenyl)propane and a combination of isophthalic and terephthalic acids; styrenics such as polystyrene and copolymers of styrene with (meth)acrylic esters; acrylonitrile-butadiene- styrene thermoplastics; (meth)acrylic polymers including homo- and copolymers of the parent acids, and/or their esters and/or amides; polyacetals such as polymethylene oxide; fully and partially fluoropolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, poly(tetrafluoroethylene/hexaflu
  • Polyamides are preferred ITPs and preferred amides are nylon-6,6, nylon-6, and a copolymer of terephthalic acid with 1 ,6-hexandiamine and 2 -methyl- 1,5-pentanediamine wherein 1,6- hexanediamine is about 30 to about 70 mole percent of the total diamine used to prepare the polymer.
  • Especially preferred polyamides are nylon-6,6, nylon-6 and a copolymer of terephthalic acid with 1 ,6-hexandiamine and 2 -methyl- 1,5- pentanediamine wherein 1,6-hexanediamine is about 50 mole percent of the total diamine used to prepare the polymer.
  • Included within the definition of ITP herein are blends of 2 or more ITPs or blends of one or more ITPs with an LCP provided that the ITP(s) is the continuous phase.
  • One or more (if present) of the ITPs may be toughened. Toughening is known in the art, and may be accomplished by adding one or more or a rubber, functionalized rubber, resin which reacts with the ITP such as an epoxy resin, or other materials. Toughened polyamides are preferred.
  • the polymers may contain other materials conventionally found in polymers, such as fillers, reinforcing agents, antioxidants, antiozonants, dyes, pigments, etc.
  • An especially useful material is a filler with high heat conductivity, which may increase the efficiency of the heat exchanger.
  • the composition of a tie layer will depend on which two polymers are on either side of it.
  • the tie layer may be an ITP functionalized or grafted to provide adhesion between the ITP and LCP layers, or may be a blend of one or more ITPs and one or more LCPs.
  • Typical thicknesses for ITP layers will range from about 0.025 to about 0.25 mm.
  • Typical thicknesses for LCP layers will be about 0.01 to about 0.1 mm.
  • Tie layers will usually be as thin as possible, consistent with their providing adhesion between polymer layers. This is usually about 0.01 to about 0.1 mm.
  • the total thickness of the structure is preferably less than about 0.7 mm, more preferably about 0.12 to about 0.5 mm, and especially preferably about 0.15 mm to about 0.4 mm.
  • Heat exchangers of many different configurations are, made and used, see for instance R. K. Shah, et al., in W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. B-3, VCH Verlagsgesellschaft mbH, Weinheim, 1988, p. 2-1 to 2-108.
  • the two most common heat exchange "elements" are the tube and the plate.
  • a tube type heat exchanger one of the fluids flow through a usually circular cross sectioned tube, while the other fluid flows on the exterior of the tube.
  • Usually many small tubes are employed to create a large heat exchange surface.
  • the tubes may be finned for more efficient heat transfer.
  • small passageways akin to small tubes, are fabricated within a plate of the heat exchange material.
  • One of the fluids flows on the inside of the passageways while the other fluid flows over the exterior surface of the plates.
  • the passageways are usually small to increase surface area, and multiple plates are often used. All of the discussion about heat exchange surface materials also applies to heat exchange panels.
  • the multilayer material described herein can be made by multilayer coextrusion of a tube, see for instance U.S. Patent 5,288,529.
  • LCPs when so extruded tend to be weak in the transverse direction (perpendicular to the long axis of the tube).
  • Such problems can be solved by using a counterrotating die for the LCP portion of the extruded tube, as described in U.S. Patents 4,963,428 and 4,966,807, and G.W. Farell, et al., Journal of Polymer Engineering, vol. 6, p. 263-289 (1986).
  • the tubes can be assembled into a full heat exchanger by inserting them into tanks with proper size holes and sealing the holes with a filler such as epoxy resin, or by heat sealing.
  • Heat exchanger plates of the layered material described herein may be made by relatively standard methods. They may be directly coextruded, complete with passages in them. A flat sheet or film may be coextruded, thermoformed into the correct shape and joined adhesively or by heat into the plate. Such coextrusions are known processes, see for instance H. Mar, et al., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., Vol. 6, John Wiley & Sons, New York, 1986, p. 608-613, ibid., Vol. 7, 1987, p. 106-127, all of which is hereby included by reference. Individual films or sheets of the ITP(s) and LCP(s) may be laminated together, then formed into a heat exchanger plate. For fabrication of a plastic heat exchanger made with plates see U.S. Patent 4,955,435.
  • the heat exchangers described herein are useful for automotive and other vehicle uses, in aircraft, as comfort heat exchangers, and various ventilating, heating and air conditioning applications. They are particularly useful as liquid- gas heat exchangers used to cool automotive gasoline or diesel engines. In that case the liquid is water, water and a glycol, or water and an alcohol.

Abstract

L'invention concerne des échangeurs thermiques formés de tubes polymères (11-16) assemblés les uns aux autres. La surface extérieure des tubes (11-16) est constituée d'un polymère à point de fusion bas pour lier thermiquement des tubes adjacents (11-16) les uns aux autres, de façon à former une plaque tubulaire (10).
PCT/CA2000/000742 1999-06-22 2000-06-21 Echangeurs thermiques formes de tubes lies thermiquement WO2000079199A1 (fr)

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US60/140,400 1999-06-22

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7077643B2 (en) 2001-11-07 2006-07-18 Battelle Memorial Institute Microcombustors, microreformers, and methods for combusting and for reforming fluids
EP1754918A2 (fr) * 2005-08-19 2007-02-21 Dana Corporation Attache de tuyaux métalliques recouverts de plastique
WO2008061588A1 (fr) * 2006-11-21 2008-05-29 Kautex Textron Gmbh & Co. Kg Agencement de ligne dans un récipient en matière plastique

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3438432A (en) * 1967-06-26 1969-04-15 North American Rockwell Plastic heat exchanger with anti-buoyancy means
EP0168558A2 (fr) * 1984-07-18 1986-01-22 Akzo Patente GmbH Procédé et dispositif pour la fabrication d'échangeurs de chaleur et/ou de matière comportant des tuyaux
US4935462A (en) * 1987-04-08 1990-06-19 Cesarino Anthony J Heat sealing of polyamides
US5195240A (en) * 1988-04-15 1993-03-23 Du Pont Canada Inc. Method for the manufacture of thermoplastic panel heat exchangers
DE19529227A1 (de) * 1995-08-09 1997-02-13 Steag Ag Speicherblock für Regenerativ-Wärmetauscher
WO1998055815A1 (fr) * 1997-06-06 1998-12-10 Shailesh Doshi Procede de formage sans solvant pour panneaux d'echangeur thermique
FR2785375A1 (fr) * 1998-10-28 2000-05-05 Valeo Thermique Moteur Sa Echangeur de chaleur a faisceau de tubes et collecteurs en materiau thermoplastique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3438432A (en) * 1967-06-26 1969-04-15 North American Rockwell Plastic heat exchanger with anti-buoyancy means
EP0168558A2 (fr) * 1984-07-18 1986-01-22 Akzo Patente GmbH Procédé et dispositif pour la fabrication d'échangeurs de chaleur et/ou de matière comportant des tuyaux
US4935462A (en) * 1987-04-08 1990-06-19 Cesarino Anthony J Heat sealing of polyamides
US5195240A (en) * 1988-04-15 1993-03-23 Du Pont Canada Inc. Method for the manufacture of thermoplastic panel heat exchangers
DE19529227A1 (de) * 1995-08-09 1997-02-13 Steag Ag Speicherblock für Regenerativ-Wärmetauscher
WO1998055815A1 (fr) * 1997-06-06 1998-12-10 Shailesh Doshi Procede de formage sans solvant pour panneaux d'echangeur thermique
FR2785375A1 (fr) * 1998-10-28 2000-05-05 Valeo Thermique Moteur Sa Echangeur de chaleur a faisceau de tubes et collecteurs en materiau thermoplastique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7077643B2 (en) 2001-11-07 2006-07-18 Battelle Memorial Institute Microcombustors, microreformers, and methods for combusting and for reforming fluids
EP1754918A2 (fr) * 2005-08-19 2007-02-21 Dana Corporation Attache de tuyaux métalliques recouverts de plastique
EP1754918A3 (fr) * 2005-08-19 2009-08-19 Dana Corporation Attache de tuyaux métalliques recouverts de plastique
WO2008061588A1 (fr) * 2006-11-21 2008-05-29 Kautex Textron Gmbh & Co. Kg Agencement de ligne dans un récipient en matière plastique

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