EP0925182A1 - Echangeurs thermiques en polymere multicouche possedant une couche barriere - Google Patents

Echangeurs thermiques en polymere multicouche possedant une couche barriere

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Publication number
EP0925182A1
EP0925182A1 EP97939901A EP97939901A EP0925182A1 EP 0925182 A1 EP0925182 A1 EP 0925182A1 EP 97939901 A EP97939901 A EP 97939901A EP 97939901 A EP97939901 A EP 97939901A EP 0925182 A1 EP0925182 A1 EP 0925182A1
Authority
EP
European Patent Office
Prior art keywords
heat exchanger
recited
polymer
layer
nylon
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Withdrawn
Application number
EP97939901A
Other languages
German (de)
English (en)
Inventor
Kenneth Earl Stevens
Pallatheri M. Subramanian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Canada Inc
Original Assignee
DuPont Canada Inc
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Filing date
Publication date
Application filed by DuPont Canada Inc filed Critical DuPont Canada Inc
Publication of EP0925182A1 publication Critical patent/EP0925182A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles

Definitions

  • This invention concerns a heat exchanger wherein the material which comprises the heat exchange surface structure contains at least one polymeric barrier layer and at least one polymeric thermoplastic layer.
  • Heat exchangers are common pieces of equipment, used in many applications, such as chemical processes, in automotive uses, household uses, and others. Heat exchangers are most commonly used to transfer heat between two fluids such as two liquids, a liquid and a gas, or between two gases. Traditionally, the materials used for the heat exchange surfaces are metals, which usually have relatively high thermal conductivities and good strength. However metals have certain drawbacks, such as high forming and assembly costs, relatively high densities and therefore high weights, and sometimes poor corrosion resistance.
  • French Patent Application 2,566,107 describes heat exchanger panels made from polymers such as polyethylene. No mention is made of layered plastics or barrier layers.
  • U.S. Patents 4,923,004, 4,955,435, 5,275,235 and 5,316,078 describe heat exchangers which employ various polyamides for the heat exchange surface materials. Barrier layers are not mentioned in these patents.
  • D. A. Reay, Heat Recovery Systems & CHP, vol. 9, p. 209-16 (1989), and I. H. Gross, Proceedings of Antec '93, p. 964-968 (1993) describe the use of polymers in heat exchangers. No mention is made of using layered polymer structures, nor of using LCPs.
  • This invention concerns, a multilayer heat exchanger containing a heat exchange surface material, said HESM comprising a polymeric barrier layer and a layer of a second polymer.
  • This invention also concerns a heat exchanger panel wherein a heat exchange surface material comprises a layer of a polymeric barrier layer and a layer of a second polymer.
  • HESM heat exchange surface material
  • FIG. 1 is a schematic drawing from the side, of an apparatus for carrying out the multilayer film forming process described herein.
  • An extruder, 1 supplies molten first thermoplastic to slit die 2 from which issues a molten multilayer thermoplastic film 3.
  • a second extruder, 34 supplies molten second thermoplastic to slit die 2.
  • a third extruder, 35 supplies molten third thermoplastic to slit die 2.
  • the molten 3 -layer film 3 falls vertically until it contacts approximately simultaneously embossed surfaces 7 and 8 of rollers 5 and 6, respectively.
  • Rolling bank 4 of thermoplastic is also present.
  • Rollers 5 and 6 are driven in rotation in the directions shown.
  • Multilayer film 9 exits the gap from between rollers 5 and 6, goes between (optional) cooling rollers 9 and 10, and is wound up on windup roll 11.
  • Figure 2 shows the same rollers 5 and 6 and rolling bank 4 from the top, together with one method of oscillating the rollers 5 and 6 parallel to the axis (center line) of each of these rollers.
  • Lever 9 is connected to a fixed point by pin 10, and to arms 13 and 14 by pins 19 and 20 respectively.
  • the arms 13 and 14 are connected to rollers 5 and 6 respectively, through thrust bearings 15 and 16 respectively, allowing rollers 5 and 6 to rotate while being oscillated.
  • Lever 9 contains slot 16 into which cam 17 is fitted.
  • Motor 18 rotates cam 17 thereby causing lever 9 to oscillate approximately 5 perpendicularly to the rotational axis of rollers 5 and 6. This causes 5 and 6 to oscillate in directions opposite to each other and parallel to their rotational axis.
  • the molten multilayer film formed in the slit die 2 is passed through rollers which oscillate along the axis of rotation of the rollers, thereby imparting a transverse (to the direction of movement of the film) shearing action to the l o molten polymer of the multilayer film.
  • Heat exchangers described herein function to exchange heat (energy) between two fluids.
  • These fluids may be gas(es) and/or liquid(s).
  • One of the materials which is part of the HESM is a polymer layer (PL).
  • polymer layer is mean a layer that is made of a natural or synthetic polymer, preferably an organic polymer. It is also preferred that the PL is a thermoplastic. Any polymer 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 barrier layer) to the HESM to 0 reasonably maintain its shape and contain the fluids in the heat exchanger, as needed, unless the HESM is deliberately designed to be flexible. 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 preferably should be reasonably chemically stable to those fluids so as to maintain its integrity.
  • a polymeric barrier layer (PBL) used in the HESM often alleviates or eliminates one or more of the above mentioned problems.
  • PBL polymeric barrier layer
  • the polymer of a PBL should have a permeability to a liquid or a gas which is 1/10 (0.10) or less, preferably about 1/100 (0.010) or less, than the permeability of the most permeable polymer layer in the multilayer structure.
  • the PBL should have a permeability to liquids of about 31 g-mil/m 2 /day (0.79 g-mm/m 2 /day) or less, preferably about 3.1 g-mil/nr/day (0.079 g-mm/m 2 /day) or less, or a permeability to gases (for a gas/gas heat exchanger) of about 100 ml-mil/m 2 /day (2.5 ml-mm/m 2 /day) or less, preferably 10 ml-mil/m 2 /day (0.25 ml-mm/m 2 /day) or less.
  • Permeability measurements on liquids to obtain these values should be at 38°C, while measurements on gases should be at 23°C.
  • the PBL is placed between a fluid and any particular PL in the HESM it often protects that PL from chemical degradation by the fluid, and/or also often protects the PL from being swollen by that fluid.
  • the commonly used internal coolant is a mixture of a glycol and water
  • the external coolant is air.
  • a PBL to the water/glycol mixture
  • Other barrier layer materials may also be used, for instance a metal in the form of a foil, a metalized surface or a ceramic in the form of a sputtered coating.
  • the PBL is often the more expensive of the polymers present in the HESM, it is usually economically preferable to limit its use. Therefore, in most constructions it is preferred that the PBL is present in relatively thin layer(s) and that layer(s) of the PL 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 PBL(s)and one or more PLs. If more than PBL and/or PL is present, more than one type of PBL and/or PL, respectively, can be used. In addition other layers may be present. For example, so called tie layers (TL), also called adhesive layers, may be used to increase the adhesion between various PBLs and PLs. or between PLs or between PBLs.
  • tie layers and PBL(s) will be relatively thin compared to the PL(s). Typical constructions are given below, wherein 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 PL, construction (a) may be particularly useful, but (c) and (f) may also be utilized. If both Fluids 1 and 2 attacked the PL present construction (c) or (f) may be particularly useful. If one wanted to minimize diffusion of one fluid to another, a construction having two PBL 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 PL, a construction such as (e) could be chosen wherein PL-1 and PL-2 have the requisite properties. These and other combinations of layers having the correct properties for various applications will be apparent to the artisan.
  • Polymers useful as PBLs will depend on what the fluids that are being heat exchanged are. Permeabilities of various polymers are known or can be measured by known methods, see for instance ASTM E 96-95, ASTM F 1249-90 and ASTM D3985- 95. These methods measure gas or vapor permeabilities, but may be readily modified to measure the permeability of liquids, by using liquids in the measurement and having them contact the polymer whose permeability is being measured. When testing the permeability of a potential barrier polymer, it is preferred that test be carried out on a single layer of the barrier polymer itself. For a list of polymer permeabilities see S. Pauly in J.
  • a polymer acts as a PBL in one particular heat exchanger, it may be only be a PL in another heat exchanger due to differing liquids in the two heat exchangers.
  • one of the heat exchange fluids is a gas and the other is a liquid (during actual heat exchanger operation) it is preferred that the barrier layer be relatively impermeable to the liquid. If both heat exchange fluids are liquids the barrier layer must be relatively impermeable to at least one fluid liquid, but is preferably relatively impermeable to both liquids. The same is true of a gas/gas heat exchanger. It is also preferred that the permeability of the barrier layer be measured under temperature conditions under which the heat exchanger typically operates.
  • One preferred heat exchanger herein is an automotive or other heat exchanger in which one fluid is water a water/alcohol mixture, or a water/glycol (such as ethylene glycol or 1 ,2-propylene glycol) mixture, and the other fluid is a gas, most commonly air.
  • the barrier layer have a low permeability to the liquid fluid, the water, water/alcohol, or water/glycol mixture.
  • Polymers which may be useful in PBLs for liquids include various polyolefins such as polyethylene, polypropylene, ethylene/carbon monoxide copolymers and various polycycloolefins, fluoropolymers such as poly(tetrafluoroethylene), polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene 2,6-napthoate), other polymers such as poly(vinyl chloride), poly(vinylidene chloride), and polyacrylonitrile.
  • polyolefins such as polyethylene, polypropylene, ethylene/carbon monoxide copolymers and various polycycloolefins
  • fluoropolymers such as poly(tetrafluoroethylene
  • polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene 2,6-napthoate)
  • other polymers such as poly(vinyl chloride), poly(vinyliden
  • polymers such as fluoropolymers such as poly(tetrafluoroethylene), polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene 2,6-napthoate), polyamides such as nylon-6,6, nylon-6. and high temperature nylons; and other polymers such as poly(vinyl chloride), poly(vinylidene chloride), polyacrylonitrile, copolymers of ethylene and vinyl alcohol, and poly(vinyl alcohol).
  • fluoropolymers such as poly(tetrafluoroethylene)
  • polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene 2,6-napthoate), polyamides such as nylon-6,6, nylon-6. and high temperature nylons
  • polyamides such as nylon-6,6, nylon-6. and high temperature nylons
  • other polymers such as poly(vinyl chloride), poly(vinylidene chloride), polyacrylonitrile, copolymers
  • LCP liquid crystalline polymers
  • Useful LCPs include those described in U.S. Patents 3,991,013, 3,991,014 4,01 1,199, 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,
  • 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'- wherein R 1 is hydrogen or hydrocarbyl, be to carbon atoms which are part of aromatic rings.
  • a PBL is a blend of 2 or more polymers having the required permeability.
  • Useful thermoplastic polymers for PLs 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), polyethylene 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
  • polystyrene resin as an ionomer of an ethylene-acrylic acid copolymer; polycarbonates; poly(amide- imides); poly(ester-carbonates); poly(imide-ethers); polymethylpentene; linear polyolefins such as polypropylene; poly(etherketoneketone); polyimides; poly(phenylene sulfide); polymers of cyclic olefins; poly(vinylidene chloride); polysulfones; poly(ether- sulfones); and polyamides such as nylon-6,6 nylon-6, nylon-6,12, nylon-6,12, nylon 4,6, l o and the polyamides from terephthalic acid and 1 ,6-hexanediamine and or 2-methyl- 1 ,5- pentanediamine.
  • Polyamides are preferred PLs 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-
  • thermosetting polymers for PLs are those that have the requisite properties as described above, and include epoxies, thermoset polyesters, and phenolics. These polymers will be formed into their final shapes before being crosslinked, as is normal with thermosetting polymers.
  • the polymers may contain other materials conventionally found in polymers,
  • An especially useful material is a filler with high heat conductivity, which may increase the efficiency of the heat exchanger.
  • composition of a tie layer will depend on which two polymers are on either side of it.
  • the tie layer may be the polymer of a PL functionalized or grafted
  • Typical thicknesses for PL layers will range from about 0.025 to about 0.25 mm.
  • Typical thicknesses for PBL 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 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 thermoplastic 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 (e.g., melt welding).
  • 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.
  • 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.
  • 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 usually water, water and a glycol, or water and an alcohol.
  • EXAMPLE 1 Small diameter tubing (-0.37 cm diameter and 250-310 ⁇ m wall thickness) was made with multilayer construction, nylon 66/LCP/nylon 66, using three extruders and a die to separately feed the different materials as separate layers.
  • the LCP was a polyester of the composition 4,4'-biphenol/hydroquinone/terephthalic acid/2,6-naphthalene dicarboxylic acid/4-hydroxybenzoic aci ⁇ 76-hydroxy-2-naphthoic acid (mole ratio 50/50/70/30/270/50).
  • the LCP layer was about 51 ⁇ m thick.
  • the tubing was sealed at one end, then filled with a 1 :1 (vol.) mixture of commercial automotive antifreeze and water, subsequently sealed at the other end and then placed in an oven maintained at 100°C.
  • the loss of the fluid with respect to time, was obtained by weighing. The loss was found to be : 0.5 gm/100 in 2 tubing surface area/day.
  • a heat exchanger was constructed from coextruded tubing (OD 0.366 cm, ID 0.328 cm) of configuration (inside of tube to outside) 64 ⁇ m HTN nylon/ 51 ⁇ m LCP (as in Example l)/76 ⁇ m HTN nylon and active surface area of 1.959 m 2 .
  • the HTN was a blend of a polyamide which is a polymer of 1 ,6-hexanediamine and 2-methyl- 1,5- pentanediamine (1:1 mole ratio) and terephthalic acid, with a synthetic rubber (Nordel® 3681, and EPDM-type rubber, available from E. I.
  • EXAMPLE 3 A film of the following composition was produced by the blown film coextrusion method: layer 1 nylon 6/Sclair® 11K1 VFusabond®
  • the LCP used was a polymer of the following monomers in the bracketed molar ratios; 4,4'-biphenol(26.3)/hydroquinone(26.3)/l,6-hexanediamine(47.4)/terephthalic acid(36.8)/2,6-naphthalene dicarboxylic acid(63.2)/4-hydroxybenzoic atid(89.5)/6- hydroxy-2-napthoic acid(36.8).
  • Melting point (DSC) of this LCP was 265°C.
  • the film was used as a "lid" of an aluminum cup containing ethylene glycol: water mixture (a used ⁇ -l : 1 ratio of commercial automotive antifreeze and water, radiator fluid), secured between metal rings and gaskets to avoid leakage and was placed in the inverted position ( so that the liquid would contact the film) in an oven at 100 C. Periodically, the cup was removed from the oven, cooled and weighed and placed back in the oven. The repeated cooling and reheating made the film concave or convex because of the pressure differences inside the cup as a consequence of the temperature variations. This induces another repeated fatigue stress which can be qualitatively observed, but was not measured.
  • ethylene glycol: water mixture a used ⁇ -l : 1 ratio of commercial automotive antifreeze and water, radiator fluid
  • the LCP used was a polymer of the following monomers in the bracketed molar ratios; 4,4'-biphenol(35.5)/hydroquinone(35.5)/l,6-hexanediamine(29.0)/terephthalic acid(60)/2,6-naphthalene dicarboxylic acid(40)/4-hydroxybenzoic acid(130).
  • the melting point (DSC) of this LCP was 255°C. 20 Evaluation as per Example 1 at 38°C showed a loss of 0.02 gm/100 in 2 /day; nylon
  • Example 5 For this example a coextruded 3 -layer film was used.
  • the melt temperature of the inner layer was 269°C
  • the melt temperature of the outer layers 25 was 292°C
  • the line speed was 14.5 m/min.
  • the inner layer which was 0.076 mm thick, was Bynel® 4006 (this is a maleic anhydride modified high density polyethylene with a melt index of 0.6, available from E. I. DuPont de Nemours & Co., Wilmington, DE, U.S.A.)
  • the two outer layers were the same polymer used for layer 1 of Example 3, and each outer layer was 0.057 mm thick.
  • the film was corona treated on both sides to 30 about 48 dynes/cm.
  • the film was formed into heat exchanger panels consisting or 13 rectangularly shaped liquid flow channels with manifolds on each end, and each panel had a primary heat exchange surface area about 54 cm long and 5 cm wide. Panels (67) were stacked by joining the manifolds, and the primary heat exchange surface of the stack was estimated to be 33,626 cm 2 .
  • a similar heat exchanger was made from single layer film 0.19 mm thick of the same polymer of the outer layers of the above heat exchanger.
  • This 69 panel heat exchanger had a surface area of about 34,632 cm 2 .
  • Polymer A was a liquid crystalline polymer which was an aromatic polyester, and was a copolymer of (molar ratios in parentheses): 4,4'- biphenol(26.3)/hydroquinone(26.3)/l,6-hexanediamine(47.4)/terephthalic acid(36.8)/2,6- naphthalene dicarboxylic acid(63.2)/4-hydroxybenzoic acid(89.5)/6-hydroxy-2-napthoic acid(36.8).
  • Polymer B was a nylon 6/Sclair® 1 lKlVFusabond® D226 b /a functionalized synthetic rubber 0 (72.5/13.6/6.8/6.8 weight percent ("LLDPE available from Nova
  • Polymer C was a blend prepared in a twin screw extruder of 40 percent by weight of Polymer A and 60 percent by weight of Polymer B.
  • Polymer A was extruded from the Wilmod extruder running at 45 rpm and the melt temperature was 280°C.
  • Polymer B was extruded from the NRM extruder running at 20 rpm and at a melt temperature of 280°C.
  • Polymer C was extruded from the Brabender extruder ⁇ inning at 60 rpm and with a melt temperature of 270°C.
  • Polymer C was the inner layer.
  • the molten film fell by gravity on the oscillating rollers, which were arranged as shown in Fig. 1.
  • the rollers were 8.9 cm in diameter and 20.3 cm wide, and the surfaces were faced with stainless steel which were embossed with a diamond or knurled pattern, about 50-75 ⁇ m deep, with a 90° included angle for the sides, with the knurling lines at an angle of 30° to the axis of rotation of the roll.
  • the rotational speeds of the rollers were manually controlled using a variable speed drive motor and was set so the surface speed of the rolls was 6m/min.
  • the rate of oscillation was also manually controlled by a variable speed drive motor and was 50 Hz, while the amplitude of oscillation could be varied by changing the cam 17, and was 1.3 mm.
  • Each roller was individually heated by Calrod® electrical heaters, which were in turn automatically controlled by digital controllers. It is believed that the roller temperatures could be maintained to about ⁇ 1°C, and the roller temperatures were 177°C. After passing through the oscillating rollers the film was passed through a set of cooling rolls and then rolled up on a roll.
  • the Polymer a layer was about 0.051 mm thick
  • the Polymer B layer was about 0.10 mm thick
  • the Polymer C layer was about 0.051 mm thick.
  • the sheets were coated on the Polymer B side with a solution of benzyl alcohol and phenol, as described in U.S. Patent 4,935,462.
  • the coated sides were placed in face- to-face contact, between female molds containing grooves parallel to the long axis of the sheets, with inlet and outlet headers at each end of the sheets.
  • the molds were then heated in a press at 160°C and 241 MPa pressure was applied while nitrogen gas was passed between the sheets so that each sheet conformed to the shape of the grooves, the two sheets were bonded together, and the headers were bonded to the ends of the sheets. No fractures or tears were evident in the resulting panel in the outer surfaces (which were Polymer A).
  • the headers of several of these panels were bonded together to form a heat exchanger.
  • An otherwise identical heat exchanger was made from 0.2 mm thick sheeting of Polymer B (the sheeting didn't go through the oscillating rollers). Water at 70°C was passed through the two heat exchangers, and the rate of water loss by diffusion through the panels measured.
  • the rate of water loss for the heat exchanger made with the three- polymer layer panels was 0.8 g/hr more than 10 times less than that of the heat exchanger made from Polymer B alone which lost about 9.1 g/hr of water.

Abstract

La présente invention concerne des structures d'échange thermique comportant au moins une couche d'un polymère organique et au moins une couche d'un polymère barrière, et dont l'usage est particulièrement recommandé partout où le poids constitue un facteur important, comme dans les automobiles, les camions et les avions.
EP97939901A 1996-09-11 1997-09-09 Echangeurs thermiques en polymere multicouche possedant une couche barriere Withdrawn EP0925182A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US906385 1978-05-16
US2593296P 1996-09-11 1996-09-11
US25932P 1996-09-11
US90638597A 1997-08-05 1997-08-05
PCT/CA1997/000647 WO1998010927A1 (fr) 1996-09-11 1997-09-09 Echangeurs thermiques en polymere multicouche possedant une couche barriere

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EP0925182A1 true EP0925182A1 (fr) 1999-06-30

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JP (1) JP2001500242A (fr)
CA (1) CA2263603A1 (fr)
WO (1) WO1998010927A1 (fr)

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CA2263603A1 (fr) 1998-03-19
JP2001500242A (ja) 2001-01-09

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