Patent Publication Number: US-2022213373-A1

Title: Heat-removing sheet

Description:
BACKGROUND 
     A coating may include a thermally active material dispersed in a binder. 
     SUMMARY 
     In some aspects of the present description, a heat-removing sheet including a plurality of endothermic particles and a chemically cured or radiation cured resin binding the endothermic particles together is provided. The heat-removing sheet includes the endothermic particles at greater than 60 weight percent, has a flexural modulus of less than 3000 MPa and a flexural strength of greater than 0.15 MPa. The heat-removing sheet is a single free-standing layer. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic cross-sectional view of a heat-removing sheet; 
         FIG. 2  is a schematic cross-sectional view of a heat-removing sheet bent to a radius of curvature R; 
         FIG. 3  is a schematic plot of the heat absorption rate of a heat-removing sheet; 
         FIG. 4  is a schematic cross-sectional view of a battery; and 
         FIGS. 5-6  are plots of heat flow rates for heat-removing sheets. 
     
    
    
     DETAILED DESCRIPTION 
     In the following description, reference is made to the accompanying drawings that form a part hereof and in which various embodiments are shown by way of illustration. The drawings are not necessarily to scale. It is to be understood that other embodiments are contemplated and may be made without departing from the scope or spirit of the present description. The following detailed description, therefore, is not to be taken in a limiting sense. 
     Conventional heat-removing sheets typically include a coating on a substrate layer where the coating includes endothermic particles. In some applications described herein, it is preferred that a heat-removing sheet have a high heat absorption rate per unit mass of the heat-removing sheet (e.g., at least 1.5 W/g, or at least 1.8 W/g, or at least 2 W/g for at least one temperature in a range of 60° C. to 170° C.). A substrate layer reduces the heat absorption rate per unit mass due to the mass of the substrate. According to some embodiments of the present description it has been found that a heat-removing sheet can be provided as a single free-standing layer that has desired mechanical properties and a high heat absorption rate per unit mass. A free-standing layer does not need a separate substrate to maintain structural integrity. 
     The heat-absorbing sheets of the present description may be used in battery applications to remove heat from a battery cell during a thermal runaway event (e.g., as has been known to occur in some lithium ion batteries). The endothermic material used in the heat-absorbing sheet may be selected to absorb heat at lower temperatures than in conventional fire protection coatings. For example, the heat-absorbing sheet may have an endothermic peak temperature in a range of 60° C. to 170° C., or 70° C. to 150° C. and/or may have an onset temperature for the endotherm in a range of 60° C. to 120° C., or 70° C. to 110° C. 
       FIG. 1  is a schematic cross-sectional view of a heat-removing sheet  100  that includes a plurality of endothermic particles  110  and a chemically cured or radiation cured resin  120  binding the endothermic particles together. In some embodiments, the heat-removing sheet  100  includes the endothermic particles  110  at greater than 60 weight percent, or greater than 70 weight percent, or greater than 80 weight percent, or greater than 85 weight percent. Here, the weight percent is based on the total weight of the heat-removing sheet  100 . In some embodiments, the heat-removing sheet  100  includes the endothermic particles  110  at greater than 55 volume percent, or greater than 60 volume percent, or greater than 65 volume percent. Here, the volume percent is based on the total volume of the heat-removing sheet  100  (e.g., length times width times an average thickness of the sheet). In some embodiments, the heat-removing sheet  100  consists essentially of the chemically cured or radiation cured resin  120  and the endothermic particles  110 . For example, the heat-removing sheet  100  may include less than 1 wt. %, or less than 0.5 wt. % of any other components. In other words, the heat-removing sheet  100  may include the chemically cured or radiation cured resin  120  and the endothermic particles  110  at no less than 99 or 99.5 percent by weight of the heat-removing sheet  100 . 
     The heat-removing sheet  100  is a single free-standing layer. The terms “free-standing” or “self-supporting” refers to a film, sheet or layer of material having sufficient structural integrity such that it is capable of being handled and/or subjected to standard manufacturing processes without a separate supporting layer. A single layer does not include any interface between different layers. If an additional element or layer were placed on the heart-removing sheet  100 , the combination of the additional element or layer and the heat-removing sheet  100  would not be a single layer, but the heat-removing sheet  100  that would be in contact with the additional element or layer would still be a single free-stranding layer. In some embodiments, the heat-removing sheet  100  is provided as a single free-standing layer that is not bonded to any other free-standing layer. 
     In some embodiments, the heat-removing sheet  100  has an average thickness in a range of 1 to 10 mm, or 2 to 8 mm, for example. 
     In some embodiments, the particles  110  are dispersed in the resin  120 . For example, the particles may be dispersed in an uncured resin which is subsequently cured in a mold to form a sheet. In some embodiments, the particles may be coated with resin and the coated particles bound together through the resin coating, for example. 
     In some embodiments, the chemically cured or radiation cured resin  120  is formed from free radical polymerizable monomers. In some embodiments, suitable free radical polymerizable monomers include monofunctional acrylates or methacrylates. Suitable monofunctional (meth)acrylates could include n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (methacrylate), 2-hydroxyethyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, methoxy poly(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate. 
     In some embodiments, the free radical polymerizable monomers may include vinyl monomers such as styrene, n-vinyl 2-pyrrolidinone, N,N dimethyl acrylamide, acrylamide, N-vinyl caprolactam, and tri allyl-1,3,5-triazine-2,3,4-trione for example. 
     In some embodiments, the free radical polymerizable resin may include multifunctional (meth)acrylates. Examples of multifunctional (meth)acrylates include 1,3-butylene glycol diacrylate, 1,4-butanedioldiacrylate, poly(ethylene glycol) di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethyloyl propane tri(meth)acrylate, and 1,6-hexanediol di(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate. In some embodiments, the chemically cured or radiation cured resin  120  is or includes radical cured resin such as ultraviolet (UV) cured acrylate. Suitable radical cured resins include UV cured aliphatic urethane acrylates. Suitable aliphatic urethane acrylates include EBECRYL  230  (available from Allnex, Frankfurt am Main, Germany), UX-0937 from Nippon Kayaku, Tokyo, Japan, and CN9009 (available from Sartomer USA, Exton, Pa.), for example. 
     In some embodiments the free radically polymerizable resin may further include chain transfer agents to control the molecular weight and crosslinking density of the resultant binder. Examples of useful chain transfer agents include but are not limited to those selected from the group consisting of carbon tetrabromide, alcohols, mercaptans, and mixtures thereof. Examples of useful chain transfer agents include 1,4-bis(3-mercaptobutylyloxy)butane) and Pentaerithrytol tetrakis (3-mercaptobutylate). 
     In some embodiments, the free radically polymerizable resin may further includes a UV radical initiator or photoinitiator. Example photoinitiators are those available under the trade designations IRGACURE and DAROCUR from Ciba Speciality Chemical Corp., Tarrytown, N.Y. and include 1-hydroxy cyclohexyl phenyl ketone (IRGACURE 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651), bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide (IRGACURE 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one (IRGACURE 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (IRGACURE 369), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907), and 2-hydroxy-2-methyl-1-phenyl propan-1-one (DAROCUR 1173) and 2,4,6-trimethylbenzoylphenyl phosphinate. 
     In some embodiments, the chemically cured or radiation cured resin  120  is or includes chemically cured silicone or chemically cured epoxy. Suitable chemically cured silicones include those prepared from two-part, Pt-catalyzed silicones (e.g., 3M IMPRINT 3 VPS Impression Material available from 3M Company, St., Paul, Minn.), or one-part moisture-cure silicone (e.g., RTV Silicone available from CRC Industries, Horsham Township, Pa.), for example. Suitable chemically cured epoxies include those prepared from two part epoxy adhesive systems such those available from 3M Company under the SCOTCH-WELD tradename (e.g., 3M Scotch-Weld Epoxy Adhesive DP100). 
       FIG. 2  is a schematic cross-sectional view showing the heat-removing sheet  100  bent to a radius of curvature R. The radius of curvature is the inner radius of the bent sheet. For example, the heat-removing sheet  100  may be bent around a cylindrical mandrel having a radius R (e.g., bent 180 degrees around the mandrel or bent along only a portion of the mandrel when a length of the sample is less than πR). In some embodiments, the heat-removing sheet  100  can be bent to an inner radius of curvature of less than 50 cm, or less than 30 cm, or less than 20 cm, or less than 10 cm, or less than 5 cm, or less than 2 cm, or less than 1 cm, or less than 0.5 cm without yielding or cracking. Typically, thinner sheets (e.g., 1-4 mm thick) can be bent to a tighter radius of curvature than thicker sheets (e.g., 6-10 mm thick) without yielding or cracking. Yielding refers to non-recoverable plastic deformation strain of at least 0.2%. Alternatively, or in addition, the bendability of the heat-removing sheet can be characterized by a degree of curvature (central angle subtended by sheet when it is bent into a cylindrical arc) that the sheet can be bent to without yielding or cracking. In some embodiments, the heat-removing sheet can be bent to a degree of curvature of at least at least 8 degrees, or at least 10 degrees, or at least 12 degrees, or at least 15 degrees, or at least 20 degrees, or at least 25 degrees, or at least 30 degrees without yielding or cracking. In some such embodiments, the heat-removing sheet has a length of less than 50 cm, or less than 30 cm, or less than 20 cm, or less than 10 cm and the degree of curvature is determined by bending the sheet into a cylindrical arc with the length of the sheet along the circumference of the arc. 
     In some embodiments, the heat-removing sheet has a flexural modulus of less than 3000 MPa and a flexural strength of greater than 0.15 MPa. In some such embodiments, the flexural modulus is less than 1000 MPa, or less than 500 MPa, or less than 300 MPa, or less than 200 MPa. In some such embodiments or in other embodiments, the flexural strength is greater than 0.2 MPa, or greater than 0.3 MPa, or greater than 0.5 MPa, or greater than 1 MPa, or greater than 2 MPa, or greater than 3 MPa. In some embodiments, the heat-removing sheet 100 has a flexural modulus of less than 300 MPa, or less than 200 MPa, or less than 100 MPa, and has a flexural strength of greater than 0.3 MPa. In some embodiments, the heat-removing sheet  100  has a flexural modulus of less than 50 MPa and a flexural strength of greater than 0.4 MPa. In some embodiments, the flexural modulus can be as low as 1 MPa, or 3 MPa, or 5 MPa, or 10 MPa, for example. In some embodiments, the flexural strength can be as high as 20 MPa, or 10 MPa, or 5 MPa, or 4 MPa, or 3.5 MPa for example. 
     Flexural modulus and flexural strength can be determined using a 3 point bend test according to the ASTM D790-17 test standard “Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials”. As described further in the Examples, in this test, the flexural strength is the maximum flexural stress sustained by the test specimen during the bending test, and the flexural modulus is the tangent modulus of elasticity (ratio of stress to corresponding strain in the elastic limit) determined in the bending test. 
     In some embodiments, the plurality of endothermic particles  110  includes at least one of a hydrate (e.g., an inorganic hydrate) or a carbonate. In some embodiments, the plurality of endothermic particles  110  is selected from the group consisting of magnesium chloride hexahydrate, magnesium sulfate heptahydrate, sodium tetraborate decahydrate, trisodium phosphate dodecahydrate, disodium hydrogen phosphate heptahydrate, aluminum sulfate octadecahydrate, calcium sulfate dihydrate, sodium metasilicate pentahydrate, aluminum trihydrate, sodium bicarbonate, magnesium carbonate trihydrate, magnesium carbonate pentahydrate, copper sulfate pentahydrate, zinc nitrate hexahydrate, sodium tetraborate decahydrate, sodium acetate trihydrate, zinc sulfate heptahydrate, aluminum chloride hexahydrate, potassium aluminum sulfate dodecahydrate, calcium chloride hexahydrate, ammonium oxalate monohydrate, boric acid, and combinations thereof. The particles  110  may have any suitable distribution of sizes (e.g., monomodal or polymodal) and any suitable mean (e.g., D 50 ) particle size (e.g., 1 micrometer to 10 mm, or 10 micrometers to 5 mm, or 100 micrometers to 2 mm). The types of particles  110  used may be selected to provide an endothermic peak temperature in a desired temperature range. 
       FIG. 3  is a schematic plot of the heat absorption rate of a heat-removing sheet, such as heat-removing sheet  100 , versus temperature. The heat absorption rate can be determined using differential scanning calorimetry (DSC). In some cases, the DSC heat absorption curve is determined by keeping a sample at 0° C. for 5 minutes and then ramping up to 300° C. at a heating rate of 10° C./min. In some embodiments, the plurality of endothermic particles  110  has an endothermic peak temperature T 1  in a range of 60° C. to 170° C., or 70° C. to 150° C. In some such embodiments, the plurality of endothermic particles has one or more additional endothermic peak temperature. For example, a second endothermic peak temperature T 2  higher than T 1  is schematically illustrated in  FIG. 3 . In some embodiments, the heat-removing sheet  100  has a heat absorption rate (e.g., H 1 ) of at least 1.5 W/g, or at least 1.8 W/g, or at least 2 W/g for at least one temperature in a range of 60° C. to 170° C. In some embodiments, the heat absorption rate is at least 1.5 W/g, or at least 1.8 W/g, or at least 2 W/g for at least one temperature in a range of 70° C. to 150° C. The area under the heat absorption rate curve is proportional to the total heat absorbed during the temperature ramp up. In some embodiments, the heat-removing sheet  100  absorbs at least 600 J/g, or at least 700 J/g, or at least 800 J/g when heated from 20° C. to 240° C. at a rate of 10° C./min. 
     In some embodiments, a battery includes a battery cell and the heat-removing sheet  100  disposed adjacent the battery cell. The battery may include one or more battery cells and a plurality of the heat-removing sheets  100 . 
       FIG. 4  is a schematic cross-sectional view of a battery  200  including a plurality of battery cells  250  and a plurality of heat-removing sheets  100 . In some embodiments, each battery cell  250  is disposed adjacent at least one (two in the illustrated embodiment) heat-removing sheet  100 . Other arrangements of battery cells known in the art may be utilized. Each of the heat-removing sheets  100  in the battery  200  is a single free-standing layer, preferably having a high heat absorption rate per unit mass of the heat-removing sheet (e.g., at least 1.5 W/g, or at least 1.8 W/g, or at least 2 W/g for at least one temperature in a range of 60° C. to 170° C.). In some embodiments, a battery includes a heat-removing sheet  100  disposed between two battery cells where a major surface of the heat-removing sheet  100  is in direct contact with each battery cell. The heat-removing sheet  100  is preferably flexible (e.g., having a flexural modulus in a range described elsewhere) so that adjacent battery cells can swell without damaging the heat-removing sheet  100 . 
     The following is a list of exemplary embodiments of the present description. 
     In a first embodiment, a heat-removing sheet comprises: 
     a plurality of endothermic particles; and 
     a chemically cured or radiation cured resin binding the endothermic particles together, wherein the heat-removing sheet includes the endothermic particles at greater than 60 weight percent, has a flexural modulus of less than 3000 MPa and a flexural strength of greater than 0.15 MPa, and wherein the heat-removing sheet is a single free-standing layer. 
     A second embodiment is the heat-removing sheet of the first embodiment, wherein the heat-removing sheet consists essentially of the chemically cured or radiation cured resin and the endothermic particles. 
     A third embodiment is the heat-removing sheet of the first or second embodiments, wherein the heat-removing sheet includes the endothermic particles at greater than 70 weight percent, or greater than 80 weight percent, or greater than 85 weight percent. 
     A fourth embodiment is the heat-removing sheet of any one of the first through third embodiments, wherein the heat-removing sheet includes the endothermic particles at greater than 55 volume percent, or greater than 60 volume percent, or greater than 65 volume percent. 
     A fifth embodiment is the heat-removing sheet of any one of the first through fourth embodiments having a flexural modulus of less than 1000 MPa, or less than 500 MPa, or less than 300 MPa, or less than 200 MPa. 
     A sixth embodiment is the heat-removing sheet of any one of the first through fifth embodiments having a flexural strength of greater than 0.2 MPa, or greater than 0.3 MPa, or greater than 0.5 MPa, or greater than 1 MPa, or greater than 2 MPa, or greater than 3 MPa. 
     A seventh embodiment is the heat-removing sheet of any one of the first through fourth embodiments having a flexural modulus of less than 300 MPa, or less than 200 MPa, or less than 100 MPa, and a flexural strength of greater than 0.3 MPa. 
     An eight embodiment is the heat-removing sheet of any one of the first through seventh embodiments, wherein the heat-removing sheet can be bent to an inner radius of curvature of less than 50 cm, or less than 30 cm, or less than 20 cm, or less than 10 cm, or less than 5 cm, or less than 2 cm, or less than 0.5 cm without yielding or cracking. 
     A ninth embodiment is the heat-removing sheet of any one of the first through eighth embodiments, wherein the plurality of endothermic particles has an endothermic peak temperature in a range of 60° C. to 170° C., or 70° C. to 150° C. 
     A tenth embodiment is the heat-removing sheet of any one of the first through ninth embodiments, wherein the heat-removing sheet has a heat absorption rate of at least 1.5 W/g, or at least 1.8 W/g, or at least 2 W/g for at least one temperature in a range of 60° C. to 170° C. 
     An eleventh embodiment is the heat-removing sheet of any one of the first through tenth embodiments, wherein the heat-removing sheet absorbs at least 600 J/g, or at least 700 J/g, or at least 800 J/g when heated from 20° C. to 240° C. at a rate of 10° C./min. 
     A twelfth embodiment is the heat-removing sheet of any one of the first through eleventh embodiments, wherein the chemically cured or radiation cured resin comprises ultraviolet (UV) cured acrylate. 
     A thirteenth embodiment is the heat-removing sheet of any one of the first through eleventh embodiments, wherein the chemically cured or radiation cured resin comprises chemically cured silicone. 
     A fourteenth embodiment is the heat-removing sheet of any one of the first through thirteenth embodiments, wherein the plurality of endothermic particles comprises at least one of a hydrate or a carbonate. 
     A fifteenth embodiment is a battery comprising a battery cell and the heat-removing sheet of any one of the first through fourteenth embodiments disposed adjacent the battery cell. 
     EXAMPLES 
       
     
       
         
           
               
            
               
                   
               
               
                 Materials Used in the Examples 
               
            
           
           
               
               
            
               
                 Abbreviation 
                 Description and Source 
               
               
                   
               
               
                 Metso 20 
                 Sodium metasilicate pentahydrate, obtained under the  
               
               
                   
                 trade designation “METSO PENTABEAD 20” from PQ  
               
               
                   
                 Corporation, Valley Forge, PA 
               
               
                 Imp3LB 
                 Two-part, Pt-catalyzed silicone, obtained under the trade  
               
               
                   
                 designation “3M ESPE IMPRINT 3 LIGHT BODY” from  
               
               
                   
                 3M Company, St. Paul, MN 
               
               
                 RTV 
                 One-part, moisture-cured silicone, “RTV Silicone Sealant- 
               
               
                   
                 Red” (Product #14059) from CRC Industries, Inc.,  
               
               
                   
                 Warminster, PA 
               
               
                 E230 
                 Aliphatic urethane diacrylate, obtained under the trade  
               
               
                   
                 designation “EBECRYL 230” from Allnex, Frankfurt,  
               
               
                   
                 Germany 
               
               
                 HEA 
                 2-Hydroxyethyl Acrylate, from BASF, Ludwigshafen,  
               
               
                   
                 Germany 
               
               
                 UX-0937 
                 Aliphatic urethane acrylate oligomer, obtained under the  
               
               
                   
                 trade designation “UX-0937” from Nippon Kayaku,  
               
               
                   
                 Tokyo, Japan 
               
               
                 TEGDA 
                 Triethyleneglycol Diacrylate, from Aldrich, Milwaukee,  
               
               
                   
                 WI 
               
               
                 SR494 
                 Ethoxylated pentaerythritol tetraacrylate, obtained under  
               
               
                   
                 the trade designation “SR494” from Sartomer (Arkema  
               
               
                   
                 Group), Colombes, France 
               
               
                 t-BA 
                 Tert-butyl acrylate, from Alfa Aesar, Haverhil, MA 
               
               
                 CN9009 
                 Aliphatic urethane acrylate oligomer, obtained under the  
               
               
                   
                 trade designation “CN9009” from Sartomer (Arkema  
               
               
                   
                 Group), Colombes, France 
               
               
                 BD1 
                 1,4-bis(3-mercaptobutylyloxy)butane) from Showa  
               
               
                   
                 Denko, Tokyo, Japan 
               
               
                 PE1 
                 Pentaerithrytol tetrakis (3-mercaptobutylate) from Show  
               
               
                   
                 Denko, Tokyo, Japan 
               
               
                 TIC 
                 Tri allyl-1,3,5-triazine-2,3,4-trione, from Aldrich,  
               
               
                   
                 Milwaukee, WI 
               
               
                 I-651 
                 2,2-Dimethyoxy-1,2,-diphenylethan-1-one, obtained  
               
               
                   
                 under the trade designation “IRGACURE-651” from  
               
               
                   
                 BASF, Ludwigshafen, Germany 
               
               
                 TPO-L 
                 2,4,6-trimethylbenzoylphenyl phosphinate, obtained under  
               
               
                   
                 the trade designation “IRGACURE TPO-L” from BASF,  
               
               
                   
                 Ludwigshafen, Germany 
               
               
                   
               
            
           
         
       
     
     Test Methods 
     Differential Scanning Calorimetry (DSC) 
     Differential scanning calorimetry analysis was performed on samples using a TA Instruments Model Q 200  differential scanning calorimeter (TA Instruments, New Castle, Del.). The sample (typically 2-10 mg) was placed in an aluminum pan (obtained under the trade designation “TZERO” from TA Instruments, New Castle, Del.) without a lid, and an empty aluminum pan without a lid was used as the reference. The sample and reference were initially cooled to 0° C. and kept at this temperature for 5 mins to equilibrate prior to ramping to 300° C. at a heating rate of 10° C./min. Measurements of heat flow versus temperature were plotted to determine the heat absorbing properties of a sample. Integration over a selected temperature range in the heat flow versus temperature curves (peaks in the negative direction of heat flow) was performed using TA INSTRUMENTS UNIVERSAL ANALYSIS  2000  software from TA Instruments, New Castle, Del., providing a measure of the amount of heat absorbed by the sample over the selected temperature range. 
     Flexural Strength and Flexural Modulus: Texture Analyzer 
     Flexural strength and flexural modulus measurements were made using a TA.XT Plus texture analyzer (Texture Technologies, Hamilton, Mass.) with the 3 point bend rig (Model TA-92N from Texture Technologies, Hamilton, Mass.). The support span was set at 50 mm and the rectangular sample was placed centered across the span. An about 3.0 mm radiused stainless steel flat probe was centered in the middle of the support span (above the sample) and compressed onto the sample at a test speed of 1.2 mm/min until the sample was broken or permanently deformed was used for all tests. Applied force and probe distance traveled were recorded to generate a load-deflection curve for each sample using EXPONENT software from Stable Micro Systems, Surrey, United Kingdom. The same software was used for Typical dimensions of tested samples were 2-3 mm×12-13 mm×˜75-76 mm. 
     Flexural strength (σ f  in MPa (psi)) was calculated at the maximum load point on the load-deflection curve using the following equation (Eqn. 3 for Flexural Stress from ASTM D790-17): 
     
       
         
           
             
               σ 
               f 
             
             = 
             
               
                 3 
                 ⁢ 
                 PL 
               
               
                 2 
                 ⁢ 
                 
                   bd 
                   2 
                 
               
             
           
         
       
     
     where:
 
P=load at a given point on the load-deflection, curve, N (lbf)
 
L=support span, mm (in.)
 
b=width of beam tested, mm (in.), and
 
d=depth of beam tested, mm (in.).
 
     Flexural modulus (tangent modulus of elasticity E B  in bending, MPa (psi)) was calculated using the following equation (Eqn. 6 for Tangent Modulus of Elasticity from ASTM D790-17): 
     
       
         
           
             
               E 
               B 
             
             = 
             
               
                 
                   L 
                   3 
                 
                 ⁢ 
                 m 
               
               
                 4 
                 ⁢ 
                 
                   bd 
                   3 
                 
               
             
           
         
       
     
     where:
 
L=support span, mm (in.),
 
b=width of beam tested, mm (in.),
 
d=depth of beam tested, mm (in.), and
 
m=slope of the tangent to the initial straight-line portion of the load-deflection curve, N/mm (lbf/in.) of deflection.
 
     Preparatory Examples 
     Preparatory Example PE1 
     A UV curable binder formulation was prepared using the following steps. 55 g of 
     EBECRYL 230, 25 g of UX-0937, and 20 g of HEA, 0.3 g of IRGACURE 651, and 0.5 g of IRGACURE TPO-L were added to an amber tinted jar and mixed for 24 hours with gentle rolling. 
     Preparatory Examples PE2-PE5 
     UV curing binder formulations PE2-PE5 were prepared in a similar manner as PE1 according to amounts used in grams in Table 1 below. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Summary of Preparatory Example Formulations 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Prep 
                   
                   
                 UX- 
                   
                   
                   
                   
                   
                   
                   
                 I- 
                 TPO- 
               
               
                 Ex. 
                 EB230 
                 HEA 
                 0937 
                 TEGDA 
                 SR494 
                 t-BA 
                 CN9009 
                 BD1 
                 PE1 
                 TIC 
                 651 
                 L 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 PE1 
                 55 
                 20 
                 25 
                   
                   
                   
                   
                   
                   
                   
                 0.3 
                 0.5 
               
               
                 PE2 
                 30 
                 20 
                 25 
                 25 
                   
                   
                   
                   
                   
                   
                 0.3 
                 0.5 
               
               
                 PE3 
                 15 
                 20 
                 15 
                 50 
                   
                   
                   
                   
                   
                   
                 0.3 
                 0.5 
               
               
                 PE4 
                   
                   
                   
                   
                 10 
                 50 
                 40 
                   
                   
                   
                   
                 0.5 
               
               
                 PE5 
                   
                   
                   
                   
                   
                   
                   
                 20 
                 4 
                 15.3 
                   
                 0.2 
               
               
                   
               
            
           
         
       
     
     EXAMPLES 
     Example EX1. Metso 20:PE1 (75:25 wt. ratio) 
     Approximately 7.5 g of Metso 20 was mixed with 2.5 g of PE1 by hand using a wooden spatula for one minute to give an intimate mixture of Metso 20 particles and resin. The mixture was then spread and compacted by hand into a circular 40 mm diameter× 3/16″ deep silicone mold, with any excess mixture being removed to provide a flat, leveled top surface of mixture in the mold. The mixture in the mold was then cured in air using a custom built 380 nm UV LED light source with an output intensity of approximately 60 mW/cm 2  at a sample-to-light source distance of approximately 4 cm for 5 mins on each face of the sheet sample to produce a flexible, free-standing heat-removing sheet. The DSC analysis of Example EX1 showed 836.3 J/g of heat absorbed between 20 and 240° C. The DSC profile for Example EX1 is shown in  FIG. 5 . The DSC profile had a peak heat flow rate of −2.08 W/g (i.e., the sample had a heat absorption rate of 2.08 W/g) at a temperature of 91.91° C. 
     Example EX2. Metso 20:PE5 (75:25 wt. ratio) 
     Approximately 18.02 g of Metso 20 was mixed with 5.99 g of PE5 by hand using a wooden spatula for one minute to give an intimate mixture of Metso 20 particles and resin. The mixture was then spread and compacted by hand into a rectangular 4 cm×11 cm× 3/16″ deep silicone mold, with any excess mixture being removed to provide a flat, leveled top surface of mixture in the mold. The mixture in the mold was then cured in air using the UV LED light source from Example EX1 at a sample-to-light source distance of approximately 4 cm for 5 mins on each face of the sheet sample to produce a flexible, free-standing heat-removing sheet. The DSC analysis of Example EX2 showed 816.7 J/g of heat absorbed between 20 and 240° C. 
     Examples EX3-EX10 and Comparative Examples CE1-CE4 
     Examples EX3-EX10 and Comparative Examples CE1-CE4 were prepared in a similar way to EX2: Metso 20 was mixed with either PE1, PE2, PE3 or PE4 in the given weight ratios noted in Table 2 by hand using a wooden spatula for one minute to give an intimate mixture of Metso 20 particles and resin. The mixture was then spread and compacted by hand into a rectangular 0.5 in×3 in×⅛ in deep aluminum mold, with any excess mixture being removed to provide a flat, leveled top surface of mixture in the mold. The mixture in the mold was then cured in air using the UV LED light source from Example EX1 at a sample-to-light source distance of approximately 4 cm for 5 mins on each face of the sheet sample to produce a flexible, free-standing heat-removing sheet. The flexural strength and flexural modulus are reported in Table 2. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Summary of Examples EX3-EX11 and Comparative Examples  
               
               
                 CE1-CE3 Formulations 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Flex. 
                 Flex. 
               
               
                   
                 wt % 
                 Prep. Ex 
                 wt % 
                 Strength 
                 Modulus 
               
               
                 Example 
                 Metso 20 
                 (PE) 
                 PE 
                 (MPa) 
                 (MPa) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 EX3 
                 70% 
                 PE1 
                 30% 
                 1.87 
                 51.9 
               
               
                 EX4 
                 70% 
                 PE2 
                 30% 
                 3.37 
                 127 
               
               
                 EX5 
                 70% 
                 PE3 
                 30% 
                 3.45 
                 207 
               
               
                 EX6 
                 80% 
                 PE1 
                 20% 
                 0.210 
                 5.47 
               
               
                 EX7 
                 80% 
                 PE2 
                 20% 
                 0.578 
                 29.0 
               
               
                 EX8 
                 80% 
                 PE3 
                 20% 
                 0.268 
                 26.2 
               
               
                 EX9 
                 80% 
                 PE4 
                 20% 
                 0.588 
                 183 
               
               
                 EX10 
                 90% 
                 PE1 
                 10% 
                 0.157 
                 6.88 
               
               
                 CE1 
                 70% 
                 PE4 
                 30% 
                 15.8 
                 3029 
               
               
                 CE2 
                 90% 
                 PE2 
                 10% 
                 0.083 
                 5.65 
               
               
                 CE3 
                 90% 
                 PE3 
                 10% 
                 0.067 
                 6.24 
               
               
                 CE4 
                 95% 
                 PE1 
                  5% 
                 0.040 
                 3.38 
               
               
                   
               
            
           
         
       
     
     Example EX11. Metso 20:Imprint 3 LB (80:20 wt. ratio) 
     Approximately 17.67 g of Metso 20 was mixed with 2.28 g of yellow paste part from Imp3LB silicone by hand using a wooden spatula for one minute to give an intimate mixture of Metso 20 particles and resin. The particle mixture was then added to 2.14 g of white paste part from Imp3LB silicone and mixed for approximately one minute. The mixture was then spread and compacted by hand into a rectangular 4 cm×11 cm× 3/16″ deep silicone mold, with any excess mixture being removed to provide a flat, leveled top surface of mixture in the mold. The mixture in the mold was then cured at room temperature in air for 30 minutes to produce a flexible, free-standing heat-removing sheet. The DSC analysis of EX11 showed 911.0 J/g of heat absorbed between 20 and 240° C. The DSC profile for Example EX11 is shown in FIG. 6. The DSC profile had a peak heat flow rate of −2.23 W/g (i.e., the sample had a heat absorption rate of 2.23 W/g) at a temperature of 112.0° C. 
     Example EX12. Metso 20:RTV (90:10 wt. ratio) 
     Approximately 10 g of Metso 20 was mixed with 2.85 g of RTV silicone by hand using a wooden spatula for one minute to give an intimate mixture of Metso 20 particles and resin. The mixture was then spread and compacted by hand into a rectangular 4 cm×11 cm× 3/16″ deep silicone mold to fit approximately ½ of the mold volume. The sample was left to cure in air over 3 days at room temperature to produce a flexible, free-standing heat-removing sheet. The DSC analysis of Example EX12 showed 1023 J/g of heat absorbed between 20 to 240° C. 
     All references, patents, and patent applications referenced in the foregoing are hereby incorporated herein by reference in their entirety in a consistent manner. In the event of inconsistencies or contradictions between portions of the incorporated references and this application, the information in the preceding description shall control. 
     Descriptions for elements in figures should be understood to apply equally to corresponding elements in other figures, unless indicated otherwise. Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a variety of alternate and/or equivalent implementations can be substituted for the specific embodiments shown and described without departing from the scope of the present disclosure. This application is intended to cover any adaptations or variations of the specific embodiments discussed herein. Therefore, it is intended that this disclosure be limited only by the claims and the equivalents thereof.