Patent Publication Number: US-10308000-B2

Title: Method for pre-preg manufacturing

Description:
DETAILED DESCRIPTION 
     Field of the Disclosure 
     The present disclosure is directed to a pre-preg molding process for manufacturing composite parts. 
     BACKGROUND 
     Pre-preg is a term for “pre-impregnated” composite fibers in which a matrix material, such as epoxy, is already present in the fiber reinforcement before molding occurs. Pre-preg manufacturing techniques are often employed to manufacture composite parts for a variety of commercial uses, including the manufacture of aircraft, for example. Composite part manufacturing using pre-preg manufacturing methods can be a rate limiting step in the production of composite products. 
     Pre-preg is currently laid up on a molds covered with a polymer parting film during the manufacture of composite parts. In conventional practice, the parting film is replaced after every part is made, which consumes manufacturing time between parts and creates material waste in the form of the disposed of parting films. Furthermore, in order to enable easy release of pre-preg, the parting films are composed of non-adhesive polymer sheets, so that the adhesion between the pre-preg and parting film is low. Due to the low adhesion, the pre-preg may slip around on the surface during placement, thereby consuming additional time. 
     Thus, there is a need in the art for improved parting films and techniques that can provide improved efficiency in pre-preg manufacturing processes. 
     SUMMARY 
     The present disclosure is directed to a method of making a composite part. The method comprises covering a mold tool for a composite part with a parting film, the parting film comprising a polymer sheet and a pressure sensitive adhesive. The parting film is positioned so that the polymer sheet is between the mold tool and the pressure sensitive adhesive. At least one layer of pre-preg is layed up on the parting film covering the mold tool to form a layed-up composite part. The pre-preg comprises an adhesive. The layed-up composite part is removed from the parting film. 
     The present disclosure is also directed to a method of preparing a mold tool for lay up of a pre-preg. The method comprises covering a surface of the mold tool with a parting film, the parting film comprising a polymer sheet and a pressure sensitive adhesive. The parting film is positioned so that the polymer sheet is between the mold tool and the pressure sensitive adhesive. The pressure sensitive adhesive is capable of adhering to at least one layer of pre-preg during a laying up process for manufacturing a composite part, and of releasing the pre-preg after the laying up process is complete. 
     It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present teachings, as claimed. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrates aspects of the present teachings and together with the description, serve to explain the principles of the present teachings. 
         FIG. 1A  shows a method for manufacturing a composite part using a pre-preg manufacturing technique, according to the present disclosure. 
         FIG. 1B  shows the continued method of  FIG. 1A  for manufacturing a composite part using a pre-preg manufacturing technique, according to the present disclosure. 
         FIG. 1C  shows the continued method of  FIGS. 1A and 16  for manufacturing a composite part using a pre-preg manufacturing technique, according to the present disclosure. 
         FIG. 2  shows a FTIR spectra of a SOLPRENE® 9618 pressure sensitive adhesive (“PSA”) coated parting film and residue after removal of the sample from the ATR crystal, according to an example of the present disclosure. All residue peaks are less than 1% the intensity of the PSA coated parting film peaks. 
         FIG. 3  shows a FTIR spectra of a CALPRENE® 540 adhesive coated parting film and residue after removal of the sample from the ATR crystal, according to an example of the present disclosure. All residue peaks are less than 1% the intensity of the PSA coated parting film peaks. 
         FIG. 4  shows a schematic drawing of a tack testing process, according to an example of the present disclosure. The parting film is on the bottom of the probe with the tunable adhesion surface facing the pre-preg. 
         FIG. 5  shows FTIR analysis of resin transfer to CALPRENE 540 adhesive, according to an example of the present disclosure. The intensity at 3365 cm −1  gives a surface concentration of &lt;1.1 μg-resin/cm 2  after 15 pre-preg contact cycles. 
         FIG. 6  is a graph of FTIR analysis of resin transfer to SOLPRENE 9618 pressure sensitive adhesive, which shows a surface concentration of &lt;1.0 μg-resin/cm 2  after 15 pre-preg contact cycles, according to an example of the present disclosure. 
         FIG. 7  shows FTIR spectra of CALPRENE 540 pressure sensitive adhesive and pre-preg resin, according to an example of the present disclosure. Insets show detail around three regions where bands from the resin in the pre-preg do not overlap with bands from the adhesive; (left inset) around 3365 cm −1  and (right inset) around 1510 cm −1  and 1145 cm −1 . 
         FIG. 8  shows an expanded view of the background region for spectra in  FIG. 7 . The offset of the baselines can be seen. The approximate locations for a two-point linear background correction are indicated. 
         FIG. 9  shows a spectrum and background in transmission for pressure sensitive adhesive with epoxy resin from the pre-preg on the surface, according to an example of the present disclosure. Bands from the resin and adhesive are indicated. The background (straight black line) was obtained from the two points shown by the dots at wavelengths of 3800 and 2200. 
         FIG. 10  shows background corrected, zero baseline, absorption spectra of pre-preg resin on pressure sensitive adhesive, the adhesive without resin and adhesive with varying amounts of resin, according to an example of the present disclosure. The inset shows the peak intensity for the C—H stretch of the adhesive. 
         FIG. 11  shows a calibration curve from standard samples of epoxy resin from pre-preg on pressure sensitive adhesive, according to an example of the present disclosure. The top axis gives resin solution concentrations from stock solution dilutions of 1:10, 1:20, 1:50, 1:100, 1:200, 1:300, and 1:500. Bottom axis gives resin surface concentration from 10 μl drops spread over 0.44 cm 2 . The circles show data points from 32 scan spectra. Open squares show data from 1024 scan spectra, used for low, &lt;1 μg/cm 2 , concentrations and to determine the detection limit as described below ( FIG. 13 ). Linear fit of the 32 scan spectra is shown for dilutions of 1:10, 1:20, 1:50, and 1:100. 
         FIG. 12  shows a calibration curve for resin transfer to adhesive for an HRL FTIR system, according to an example of the present disclosure. Resin surface concentration from IR intensity at 3365 cm-1; best fit (solid line), ±1σ upper and lower limits (dashed lines). 
         FIG. 13  shows a low concentration of pre-preg resin on CALPRENE 540 adhesive, according to an example of the present disclosure. Spectra are shown for standard samples from dilutions of 1:200 (dotted lines, 2 spectra) and 1:500 (dashed line). After background correction, intensities for the adhesive (2800 cm −1  to 3100 cm −1 ) overlay to within &lt;5%. Inset shows region for resin absorption on an approximately 50× expanded scale. 
     
    
    
     It should be noted that some details of the figures have been simplified and are drawn to facilitate understanding rather than to maintain strict structural accuracy, detail, and scale. 
     DESCRIPTION 
     Reference will now be made in detail to the present teachings, examples of which are illustrated in the accompanying drawings. In the drawings, like reference numerals have been used throughout to designate identical elements. In the following description, reference is made to the accompanying drawings that form a part thereof, and in which is shown by way of illustration specific examples of practicing the present teachings. The following description is, therefore, merely exemplary. 
     The present disclosure is directed to a method for manufacturing a composite part using pre-preg manufacturing techniques. Referring to  FIGS. 1A to 1C , the method involves covering a surface of a mold tool  102  with a parting film  104  comprising a polymer sheet  106  and a pressure sensitive adhesive  108 . The pressure sensitive adhesive  108  can be in any suitable form that will provide the desired adhesion between the parting film  104  and the pre-preg, such as a layer deposited or otherwise attached to the polymer sheet  106 . Referring to  FIG. 1B , at least one layer of pre-preg  110  is layed up on the parting film  104  to form a layed up composite part  112 . The pressure sensitive adhesive  108  allows the at least one layer of pre-preg  110  to adhere to the parting film  104  during the process, while having the ability to be removed from the pre-preg without leaving detrimental amounts of residue or otherwise damaging the composite part that is formed from the pre-preg. 
     As shown in  FIG. 1C , after the lay up process is complete, the molded composite part  112  is removed from the parting film  104 . During removal of the composite  112 , the adhesive force holding the composite part  112  to the pressure sensitive adhesive is overcome by applying a force that is greater than the adhesive force to pull the composite part  112  from the pressure sensitive adhesive. The laying up step of  FIG. 1B  and the removing step of  FIG. 1C  can be carried out any number of times, such as one or a plurality of times, to form a desired number of composite parts  112  without removing the parting film  104  from the mold tool  102 . As an example, the laying up step and the removing step can be carried out 5 to 50 times, such as 10 to 30 times or 15 to 25 times. 
     The pre-preg  110  can be any suitable pre-preg. Pre-pregs are well known in the art and generally comprise fibers in an adhesive resin. As an example, the pre-preg can comprise a carbon fiber reinforced plastic and/or one or more epoxy chemical groups that effectively act as an adhesive for adhering multiple pre-pregs together. The epoxy of the pre-preg also potentially adheres to other materials, such as the pressure sensitive polymer adhesive  108  of the parting film. As an example, the epoxy based pre-preg employed in the processes of the present disclosure can be said to have a threshold adhesive strength against a steel plate of greater than 10 kPa, such as about 30 to about 120 kPa, where the adhesive strength is measured using the tack test as described below with respect to  FIG. 4 , except that the steel probe is used without attaching a parting film  104 . 
     The polymer sheet  106  can comprise any non-adhesive polymer material that is non-adhesive to the pre-preg  110  and that has the structural ability to act as a standalone substrate, conform to the mold surface and withstand other pre-preg processing conditions. The polymer sheet  106  generally does not contain acrylics, rubber, styrene-butadiene-styrene copolymers or other styrene copolymers. For example, suitable non-adhesive polymer sheets can comprise a material chosen from the polymers of polyethylene, polyethylene terephthalate (“PET”), fluorinated ethylene propylene (“FEP”), nylon and combinations thereof. The thickness of the polymer sheet  106  can range, for example, from 0.0001 to 0.01 inches, such as 0.001 to 0.004 inches. 
     The term “pressure sensitive adhesive” is defined herein to designate a distinct category of adhesive material that in a dry form (e.g., substantially free of both solvent and water) are aggressively and permanently tacky at room temperature and that firmly adhere to a variety of dissimilar surfaces at room temperature, including paper, plastic, glass, wood, cement and metal, upon mere contact without the need of more than 20 pounds per square inch of pressure being applied. These products require no activation by water, solvent or heat in order to exert a strong adhesive holding force toward such materials. They have sufficient cohesive holding power and an elastic nature so that despite their aggressive tackiness, they can be handled with the fingers and removed from smooth surfaces without leaving a significant residue. The phrase “substantially free” is defined herein to mean 5% by weight or less relative to the total weight of the composition. In an example, the “pressure sensitive adhesive” can have 0 to 5% combined weight of both solvent and water, such as 0 to about 3% by weight based on the total weight of the composition. 
     The pressure sensitive adhesive has the ability to conform to the surface of the pre-preg under pressure, thereby increasing surface area contact and, in turn, the Van der Waal forces between the adhesive and the pre-preg. It is believed that the increased Van der Waals forces provide the primary mechanism for adhesion. Because the adhesive can be applied in a dry form, drying or curing of the adhesive is not necessary to accomplish the desired adhesive force. Significant adhesion is not accomplished by chemical bonding, such as covalent or ionic chemical bonding, between the surfaces, as would occur with a dried or cured adhesive. 
     The pressure sensitive adhesive  108  is chosen to have the property of adhering to the pre-preg  110  sufficiently so as to significantly reduce slipping during lay up while, at the same time, having the ability to release the composite part  112  after lay-up is completed, without damaging the composite part (e.g., without pulling out carbon fiber or transferring material to pre-preg that will change the cured part properties in an undesirable manner). As an example, the pressure sensitive adhesive can have a peak tensile strength (kPa) between the pre-preg  110  and the adhesive coated parting film  104  of about 1 kPa to about 500 kPa peak adhesion force, such as about 3 kPa to about 50 kPa peak adhesion force, or about 5 kPa to about 25 kPa peak adhesion force, where the peak adhesion force is determined as describe herein with respect to  FIG. 4 . 
     The thickness of the pressure sensitive adhesive  108  can range, for example, from 0.0001 to 0.01 inches, such as 0.001 to 0.004 inches, or 0.001 to 0.002 inches. The pressure sensitive adhesive  108  of the parting film  104  can be reusable over multiple lay-up cycles to save the labor and waste of using a new parting film for every part. In addition, the pressure sensitive adhesive can have a glass transition temperature below 20° C., such as about negative 150° C. to about 0° C. or about negative 100° C. to about negative 50° C.; and can have greater than a 50% elasticity at room temperature (e.g., sufficient elasticity at 20° C. so as to be capable of exhibiting greater than 50% extension), such as about 100% to about 1000% elasticity. It is believed that the high elasticity can allow the material to hold together during release, thereby reducing the amount of adhesive residue that remains on the composite part. 
     The pressure sensitive adhesive can comprise linear or branched, random or block polymers having one, two, three or more monomer units. Example pressure sensitive adhesives can comprise a material chosen from the adhesives of acrylic resin, polyurethane, rubber, styrene-butadiene-styrene copolymers, ethylene vinyl acetate, styrene block copolymers, and combinations thereof, such as Styrene-ethylene/butylene-styrene (SEBS) block copolymer, Styrene-ethylene/propylene (SEP) block copolymer, Styrene-isoprene-styrene (SIS) block copolymer, or combinations thereof. As an example, the pressure sensitive adhesive comprises a material chosen from the adhesives of styrene-butadiene-styrene block copolymers, styrene-butadiene-styrene random copolymers and combinations thereof. 
     The pressure sensitive adhesive can include a block copolymer having a first block and a second block, the first block having a glass transition temperature of less than 20° C. and the second block having a glass transition temperature of greater than 20° C. Styrene-butadiene copolymers are one such example, where butadiene is a monomer that forms a polymer with a glass transition below room temperature while polystyrene has a glass transition temperature of 90-100° C. Specific examples of such polymers are shown in Table 2 below. 
     The polymer of the pressure sensitive adhesive can have a relatively high molecular weight to reduce or eliminate residue from the pressure sensitive adhesive transferring to the pre-preg during processing. As an example, the mass average molecular weight can be about 70,000 g/mol to about 1,500,000 g/mol, such as about 80,000 g/mol to about 1,200,000 g/mol, or about 100,000 g/mol to about 1,000,000 g/mol. 
     The amount of block copolymer in the pressure sensitive adhesive can be any suitable amount that will provide the desired properties. As an example, the amount of block copolymer can range from 50% to 100% by weight of the pressure sensitive adhesive, such as 80% to 99%, or 90% to 96% by weight, based on the total weight of the pressure sensitive adhesive. Because the adhesive is not dried or cured, the range of copolymer can be approximately the same both before and during adhesion of the pressure sensitive adhesive to the pre-preg, as well as after release of the composite part from the adhesive. 
     The compositions of the present disclosure can be additive free, meaning that only block copolymer is employed as the adhesive. Alternatively, in addition to the block copolymers describe herein, the pressure sensitive adhesives of the present disclosure can optionally include any other suitable ingredients in any desired amounts, such as carrier liquids, plasticizers, tackifiers, oxidation stabilizers and UV stabilizers and other such components to manage viscosity, adhesion strength, the ability to retain moisture content over time and other desired properties. Ingredients not expressly recited in the present disclosure can be limited and/or excluded from the pressure sensitive adhesive disclosed herein. Thus, the amounts of the thermoplastic polymer and any optional ingredients, such as carrier liquid, plasticizer, tackifiers, oxidation stabilizers and/or UV stabilizers can add up to 90% to 100% by weight of the total ingredients employed in the composites of the present disclosure, such as 95% to 100% by weight, or 98% to 100% by weight, or 99% to 100% by weight, or 100% by weight of the total ingredients. 
     As mentioned above, release of the composite part from the pressure sensitive adhesive is accomplished by applying sufficient tensile force to overcome the Van der Waals attraction between the composite part and the pressure sensitive adhesive. When applying force to release the composite part, the pressure sensitive adhesive will stretch as it pulls away from, thereby progressively reducing the shared surface area with the composite part, while still holding together so as to fail at the interface between the composite part and the adhesive. The elasticity allows the composite part to be more easily removed and helps to limit the amount of residue that remains on the composite part. 
     Referring again to  FIG. 1C , removal of the layed-up composite part  112  can be performed in any suitable manner. For example, removal can be performed with a tool that adheres to the composite part  112  more strongly than does the pressure sensitive adhesive  108  of the parting film. For example, the tool can be a vacuum chuck. As another example, the tool can have a surface comprising an adhesive that adheres with sufficient strength to the composite part  112  so as to be able to separate it from the parting film  104 . 
     After removal of the composite part form the mold, little or no pressure sensitive adhesive remains on the composite layer. As an example, less than 10 micrograms/cm 2  of the pressure sensitive adhesive remains on a surface  114  of the completed part that was in contact with the pressure sensitive adhesive  108  during laying up of the pre-preg  110 . As another example, less than 5 micrograms/cm 2 , such as less than 2 micrograms/cm 2  or less than 1.5 micrograms/cm 2 , of the pressure sensitive adhesive  108  remains on the surface  114  of the completed part. The amount of residue can be determined using the residue analysis procedure as described in Example 3 below. 
     The parting film  104  can be made by any suitable method. For example, the pressure sensitive adhesive can be applied onto a polymer sheet  106  using coating techniques for polymer deposition. A variety of polymer coating techniques are known in the art. If desired, the polymer sheet can be plasma-treated to improve adhesion between the non-adhesive polymer material and the pressure sensitive adhesive  108 . Any suitable plasma treatment techniques for improving adhesion can be used. Techniques for plasma treating polymer films and other substrates are generally well known in the art. Corona treatment, for example, is a common industrial plasma treatment procedure that occurs in film coating production lines. 
     EXAMPLES 
     Example 1—Sample Preparation and Adhesion Properties 
     Pressure sensitive adhesives were applied on non-adhesive parting film substrates using the following process. The adhesives and the parting film substrates are listed in Table 1 below. Parting film substrates were first Corona treated or plasma treated to improve adhesion between the pressure sensitive adhesives and the parting film substrate to prevent delamination during removal of pre-preg. Adhesives were coated onto the Corona treated parting film substrates as solutions in toluene at a loading of 37 g/m 2  (one sample was made at 25 g/m 2 ). 
     Example 2—Sample Preparation and Adhesion Properties 
     Adhesion (e.g., tack) measurements for the prepared samples were made as follows: Mode 1 tack was measured using a Malvern Kinexus rheometer with a 0-50 N load cell. Pre-preg samples one day out of the freezer were preconditioned at 55% relative humidity (“RH”) and 72° F. for 4 h. The pre-preg used for testing in the present disclosure was a Toray 3900-2/T800S type pre-preg comprising an intermediate modulus (“IM”) carbon fiber and epoxy resin. A parting film including pressure sensitive adhesive was attached to a flat, 8 mm diameter round steel probe and pre-preg was adhered to the rheometer bottom plate. The tack test was performed by bringing the probe down onto the sample, applying pressure equivalent to 12″ of mercury on the sample with the probe for 30 seconds, and pulling up the probe at 1 mm/s ( FIG. 4 ). As shown in Table 1, the tested pressure sensitive adhesives show a wide range of adhesion levels to pre-preg. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Pressure sensitive adhesives on parting films 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                 Peak tensile 
                 Adhesion 
               
               
                   
                   
                   
                 strength (kPa) 
                 energy (μJ/cm2) 
               
               
                   
                   
                   
                 between pre- 
                 between pre- 
               
               
                   
                   
                   
                 preg and 
                 preg and 
               
               
                 Adhesive  
                 Adhesive 
                 Parting film 
                 adhesive coated 
                 adhesive coated 
               
               
                 candidate 
                 chemistry 
                 substrate 
                 parting film 
                 parting film 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Dynasol SOLPRENE 
                 Poly(styrene- 
                 Plasma treated 
                 21.4 
                 0.34 
               
               
                 1205 
                 butadiene- 
                 FEP 
                   
                   
               
               
                   
                 styrene) rubber 
                   
                   
                   
               
               
                 Dynasol SOLPRENE 
                 Poly(styrene- 
                 PET 
                 12.4 
                 0.17 
               
               
                 1205 
                 butadiene- 
                   
                   
                   
               
               
                   
                 styrene) rubber 
                   
                   
                   
               
               
                 Elvax 4310 
                 Ethylene vinyl 
                 PET 
                 101.7 
                 2.99 
               
               
                   
                 acetate 
                   
                   
                   
               
               
                 Kuraray Septone 
                 Hygrogenated 
                 Plasma treated 
                 31.9 
                 0.61 
               
               
                 2063 
                 styrenic block 
                 FEP 
                   
                   
               
               
                   
                 copolymer 
                   
                   
                   
               
               
                 Kuraray Septone 
                 Hygrogenated 
                 PET 
                 49.2 
                 0.87 
               
               
                 2063 
                 styrenic block 
                   
                   
                   
               
               
                   
                 copolymer 
                   
                   
                   
               
               
                 Lubrizol HP 4080-20 
                 Polyurethane 
                 Plasma treated 
                 105.6 
                 3.56 
               
               
                   
                   
                 FEP 
                   
                   
               
               
                 Lubrizol HP 4080-20 
                 Polyurethane 
                 PET 
                 56.8 
                 1.35 
               
               
                 Ashland Aroset 1450 
                 Acrylic pressure 
                 FEP 
                 95.0 
                 4.30 
               
               
                   
                 sensitive 
                   
                   
                   
               
               
                   
                 adhesive 
                   
                   
                   
               
               
                 Ashland Aroset 1450 
                 Acrylic pressure 
                 PET 
                 PSA transferred 
                 N/A 
               
               
                   
                 sensitive 
                   
                 to pre-preg 
                   
               
               
                   
                 adhesive 
                   
                   
                   
               
               
                 Avery Dennison 
                 Hot melt adhesive 
                 FEP &amp; PET 
                 PSA transferred 
                 N/A 
               
               
                 H210 
                   
                   
                 to pre-preg 
                   
               
               
                 Cattie 8333 
                 Hot melt adhesive 
                 FEP &amp; PET 
                 PSA transferred 
                 N/A 
               
               
                   
                   
                   
                 to pre-preg 
                   
               
               
                 Kuraray Kurarity LA 
                 Block polymer of 
                 FEP &amp; PET 
                 PSA transferred 
                 N/A 
               
               
                 2140 
                 ethyl methacrylate 
                   
                 to pre-preg 
                   
               
               
                   
                 and butyl acrylate 
                   
                   
                   
               
               
                 Nipol DM 1201 
                 Terpolymer of 
                 PET 
                 PSA transferred 
                 N/A 
               
               
                   
                 acrylonitrile, 
                   
                 to pre-preg 
                   
               
               
                   
                 butadiene and 
                   
                   
                   
               
               
                   
                 isoprene 
               
               
                   
               
            
           
         
       
     
     SOLPRENE® 1205, a Poly(styrene-butadiene-styrene) rubber, on PET and plasma treated FEP were selected for further testing because they had the lowest adhesion. It was shown using infrared spectroscopy this material was transferring to pre-preg after contact. SOLPRENE 1205 has an average molecular weight of 52,000 g/mol. Thus higher molecular weight styrene-butadiene-styrene polymer adhesives were tested as shown in Table 2. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Higher molecular weight adhesives tested 
               
            
           
           
               
               
               
            
               
                   
                   
                 Peak tensile strength 
               
               
                   
                   
                 (kPa) between pre-preg 
               
               
                 Adhesive  
                 Adhesive chemistry 
                 and adhesive coated 
               
               
                 candidate 
                 and molecular weight 
                 parting film 
               
               
                   
               
               
                 SOLPRENE 4302 on 
                 33% styrene 
                 68 
               
               
                 corona treated WL3800 
                 67% butadiene 
                   
               
               
                 PET 
                 Block polymer 
                   
               
               
                   
                 Mw = 110k g/mol 
                   
               
               
                 CALPRENE 500 on 
                 30% styrene 
                 49 
               
               
                 corona treated WL3800 
                 70% butadiene 
                   
               
               
                 PET 
                 Random polymer 
                   
               
               
                   
                 Mw = 110k g/mol 
                   
               
               
                 SOLPRENE 9618 on 
                 31% styrene 
                 43 
               
               
                 corona treated WL3800 
                 69% butadiene 
                   
               
               
                 PET (37 g/m 2  adhesive) 
                 Block polymer 
                   
               
               
                   
                 Mw = 800k g/mol 
                   
               
               
                 SOLPRENE 9618 on 
                 31% styrene 
                 42 
               
               
                 corona treated WL3800 
                 69% butadiene 
                   
               
               
                 PET (25 g/m 2   
                 Block polymer 
                   
               
               
                 adhesive) 
                 Mw = 800k g/mol 
                   
               
               
                 CALPRENE 540 on 
                 40% styrene 
                 21 
               
               
                 corona treated WL3800 
                 60% butadiene 
                   
               
               
                 PET 
                 Multi arm random 
                   
               
               
                   
                 polymer 
                   
               
               
                   
                 Mw = 110k g/mol 
               
               
                   
               
            
           
         
       
     
     The main conclusions from Table 2 are as follows:
         CALPRENE® 540 and SOLPRENE® 9618 were the most attractive samples.
           CALPRENE 540 has a desirable 21 kPa peak adhesion force tack.   SOLPRENE 9618 has the second lowest peak adhesion force.   
           Using higher molecular weight adhesives reduced the residue. No or substantially no material was transferred to pre-preg when the molecular weight was &gt;100000 g/mol.   Transitioning from a block polymer structure to a random co-polymer at constant molecular weight also decreased adhesion (SOLPRENE 4302 vs CALPRENE 500).       

     Except for SOLPRENE 9618, all of the PSAs of Table 2 are formed from linear polymers. SOLPRENE 9618 has branch points where additional polymer chains grow off the main chain, thus it is a “multi-arm” type branched polymer. Further, SOLPRENE 9618 is a random polymer that is highly extensible and has a glass transition temperature below room temperature (e.g., has a glass transition temperature of −89° C. and will undergo 850% elongation without breaking). Both CALPRENE and SOLPRENE are commercially available from Dynasol LLC of Houston, Tex. 
     Example 3—Residue Analysis 
     Residue analysis was performed to investigate the propensity for material transfer from a pressure sensitive adhesive coated parting film to pre-preg during lay-up. The procedure for this test consisted of pressing a material, in this case one of the PSA coated parting films of Table 2, against an FTIR ATR crystal, collecting a 128 scan absorbance spectrum of the material, removing the material, and collecting a 128 scan absorbance spectrum of the residue on the ATR crystal. The residue of SOLPRENE 9618 is shown in  FIG. 2  and CALPRENE 540 is shown in  FIG. 3 . In both cases the residue peak intensity is &lt;1% of the adhesive peak intensity, which is an insignificant residue level. 
     Example 4—Reusability Data 
     In order to test reusability for up to 15 lay-up cycles, a method was developed to quantify resin transfer from pre-preg to the pressure sensitive adhesive coated parting film. Resin transfer increases adhesion between parting films and pre-preg, which can result in fiber pull out from the pre-preg if a parting film is reused multiple times. Resin transfer was tested by applying a set pressure between a pressure sensitive adhesive coated parting film and pre-preg, as is discussed in greater detail below. Multiple cycles of resin transfer were performed between pre-preg and CALPRENE 540 and SOLPRENE 9618 followed by a tack test and measuring the resin level on the pressure sensitive adhesive treated parting film, as is also discussed in greater detail below. It should be noted that the tack test was an additional pre-preg contact cycle, thus a sample that has 16 cycles in Table 3 underwent 15 pre-preg contact cycles. Likewise, a sample that has 2 cycles in Table 3 underwent 1 pre-preg contact cycle before the tack test while a sample that underwent one pre-preg contact cycle only experienced a tack test followed by measuring the resin level on the film. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Resin surface concentration and tack after pre-preg contact cycles 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 Peak adhesion 
                 Adhesive energy 
               
               
                 Sample (# of 
                 Resin 
                 strength between 
                 between coated 
               
               
                 pre-preg contact 
                 concentration 
                 coated parting 
                 parting film 
               
               
                 cycles including 
                 on surface 
                 film and pre-preg 
                 and pre-preg 
               
               
                 the tack test) 
                 (μg/cm 2 ) 
                 (kPa) 
                 (μJ/cm 2 ) 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 CALPRENE 540 
                 &lt;1.0 
                 21 
                 0.3 
               
               
                 (1) 
                   
                   
                   
               
               
                 CALPRENE 540 
                 &lt;1.2 
                 14 
                 0.8 
               
               
                 (2) 
                   
                   
                   
               
               
                 CALPRENE 540 
                 &lt;1.2 
                 26 
                 0.6 
               
               
                 (16) 
                   
                   
                   
               
               
                 CALPRENE 540 
                 &lt;1.0 
                 15 
                 0.4 
               
               
                 (2) duplicate 
                   
                   
                   
               
               
                 CALPRENE 540 
                 &lt;1.0 
                 7 
                 0.1 
               
               
                 (16) duplicate 
                   
                   
                   
               
               
                 SOLPRENE 9618 
                 &lt;1.2 
                 42 
                 0.8 
               
               
                 (1) 
                   
                   
                   
               
               
                 SOLPRENE 9618 
                 &lt;1.0 
                 10 
                 0.3 
               
               
                 (2) 
                   
                   
                   
               
               
                 SOLPRENE 9618 
                 &lt;1.6 
                 17 
                 1.0 
               
               
                 (16) 
               
               
                   
               
            
           
         
       
     
     In Table 3, the peak adhesion strength is maintained at &lt;30 kPa for multiple pre-preg contact cycles for all samples. Thus extra resin on the film does not increase adhesion as is observed with bare parting films (non-adhesive polymer substrates without the PSA coating). Based on these results, PSA coated parting films are reusable. 
     To simulate multiple pre-preg lay-ups on the same surface and investigate the extent of resin transfer from pre-preg to the pressure sensitive adhesive coated parting film reported in Table 3 above, pre-preg contact cycles were conducted with test coupons of CALPRENE 540 and SOLPRENE 9618 (the two best performing pressure sensitive adhesives). For each cycle, a 25 mm diameter disk of adhesive coated parting film was laid adhesive-up on an optical glass flat. An ˜30 mm×30 mm square piece of pre-preg was laid over the adhesive. The piece of pre-preg still contained the backing sheet, which was facing up. Next a second optical glass flat was laid on the pre-preg completing the stack. To simulate the contact, a 2 kg weight was placed on the stack for 1 minute. This mass is equivalent to ˜300 mm Hg. For multiple cycles, the weight was removed and the pre-preg peeled off the adhesive coated parting film and a new piece of pre-preg was used and the process repeated. Up to 15 cycles (with a single coupon of adhesive coated parting film) were performed. 
     To determine the amount of resin transfer, FTIR spectroscopy was used to measure the resin surface concentration after 1× and 15× pre-preg contact cycles for CALPRENE 540 and SOLPRENE 9618 adhesives on Corona treated PET parting film. Selected results for the CALPRENE adhesive are shown in  FIG. 5 . After 15× pre-preg contact cycles, the IR shows essentially no peak for the pre-preg resin. Although lacking a peak, the IR intensity is increased relative to the Caplrene 540 adhesive control. The origin of this increased intensity is not fully understood but may originate from surface roughness changes due to contact with the pre-preg. Despite seeing no clear peak from the resin, simply using the IR intensity near 3365 cm −1  gives a surface concentration of &lt;1.1 μg-resin/cm 2 , which is close to our estimated detection limit for the IR measurement. The results for 15× cycles with SOLPRENE 9618 are shown in  FIG. 6 . For this test, a clear peak from the resin is seen, although it is slightly shifted from the peak in the CALPRENE standard. The cause of this shift is not understood. Nevertheless, using the peak intensity gives a surface concentration of &lt;1.0 μg-resin/cm 2 . 
     Additional details regarding the resin transfer quantification method will now be discussed. Use of IR spectroscopy to quantify resin build-up on the adhesive requires at least moderately strong adsorption bands from the resin that do not significantly overlap with bands from the adhesive. FTIR spectra of the as-received CALPRENE 540 adhesive and a piece of pre-preg (pressed with force against the ATR plate) are shown in  FIG. 7 . The spectrum of the pre-preg has several bands from the resin that do not overlap with bands from the adhesive. For the band at 3365 cm −1 , there are no nearby bands from the adhesive and the intensity in that region is featureless ( FIG. 7 , left inset). Two other bands without significant overlap occur at 1145 cm −1  and 1510 cm −1  ( FIG. 7 , right inset). The band at 3365 cm −1  is only about 20% as strong as the bands at 1145 cm −1  and 1510 cm −1 . However, these bands are not as favorable as the band at 3365 cm −1  because there is a weak band from the adhesive near 1145 cm −1  and a relatively strong band near 1510 cm −1 . For the analysis method described herein, the band at 3365 cm −1  was used. 
     As seen, for example, in  FIG. 7  and in detail in  FIG. 8 , the baselines for different spectra can differ by up to ˜0.01 absorbance units. While small, this difference is unacceptable for accurate quantification of small amounts of resin build-up on the adhesive surface. To account for this difference, a two point linear background was subtracted from the spectra. The preferred locations of the background points at ˜3800 cm −1  and ˜2200 cm −1  are shown in  FIG. 8 . 
     Prior to subtracting the background, the spectra intensity were converted from absorbance [I(abs)] into transmission [I(trans)] using the standard relationship, I(trans)=10 −I(abs) , so that intensity changes could be linearly related to concentration. An example, of a spectrum containing resin deposited on the adhesive (as described below) in transmission together with and linear background is shown in  FIG. 9 . A linear background was found to fit the spectra well over the region 2000 cm −1  to 4000 cm −1 , which contains the preferred band for quantifying the resin (3365 cm −1 ) and C—H stretch bands from the adhesive (major band at 2916 cm −1 ). 
     To obtain a background corrected spectrum in transmission but displayed with a zero (as opposed to a unity or 100%) baseline designated as ((trans, background corrected, zero baseline), the spectra was subtracted from the background [I(background)] using I(trans, background corrected, zero baseline)=I(background)−I(trans). For example, in  FIG. 9 , the straight line background between the two data points minus the lower spectrum shown in the graph. 
     Several examples of the resulting spectra are shown in  FIG. 10 . With this conversion to transmission and background correction, the baselines for most spectra taken, e.g.,  FIG. 10 , are nearly indistinguishable. Importantly, the band at 3365 cm −1  from resin build-up is clearly seen with transmission intensity spanning at least a factor of 20 relative to a common baseline. This enables the amount of resin on the adhesive to be quantified, as described below. Ideally, these transformations would also yield indistinguishable peak intensities for the adhesive. However, as shown in the inset to  FIG. 10 , the peak intensity for the main C—H stretch at 2916 cm −1  varies by 10%, from 0.20 to 0.22. Thus, an additional multiplicative normalization could be applied to the spectra. This was not done because the variability is relatively small, only ˜10%. 
     Using spectra such as those shown in  FIG. 10 , resin build-up on the adhesive may be quantified by determining a calibration curve for the peak intensity at 3365 cm −1 , (e.g., intensity versus resin concentration). This calibration curve is determined by measuring spectra for a set of resin-on-adhesive calibration samples, which have independently known resin concentrations. To fabricate calibration samples, standard solutions of resin dissolved in acetone were prepared as follows. 
     A stock solution of pre-preg resin dissolved in acetone was prepared by sonicating a 0.7 g sample of pre-preg in 30 g of acetone in a sealed vial for ˜5 min. Immediately after sonication the acetone solution was still cloudy. The sample was allowed to sit for ˜3 days during which time the solution cleared. The solution was then poured off from the remaining pre-preg to fix the resin concentration. The resin concentration was determined by evaporating 5.2516 g of solution in a 60° C. oven. A residual weight due to the resin of 0.0356 g was obtained. Thus, the stock solution had a concentration of 0.0068 g-resin/g-solution. 
     To deposit resin onto the adhesive several procedures were evaluated. The two most important and related criteria for evaluating the procedures are 1) spatially uniformity over the ATR plate area and 2) reproducible intensity of the resin band at 3365 cm −1  for nominally identical resin concentration samples. 
     The procedure selected used diluted resin/acetone solutions deposited as many small droplets onto heated samples of the adhesive. A 10 μl capillary pipette was used with small drops dabbed over a chosen area by repeatedly lightly touching the end of the capillary to the adhesive. The pipette was used without a plunger and was filled by capillary action. Each “dab” was roughly estimated to deposit &lt;˜0.5 μl, ˜20 droplets for 10 μl of the resin solution. Each drop spread over only a small portion of the area, so the overall uniformity was achieved by distributing these droplets over the ATR area by hand. In addition, the adhesive substrates were heated by being laid on a hot plate set at 70° C. In contrast, if a full 10 μl drop was deposited in a single step using the pipette with the plunger, evaporation of the drop was not uniform. As the drop evaporated, it would break up into smaller drops with the result that the deposited resin (which could be discerned optically) ended up in small concentrated spots, often near the edges of the initial drop. Using many small droplets mitigated this problem, although uniformity remained an issue. The measured IR intensities still had considerable scatter but averaging ˜5 samples for each resin concentration appeared to give consistent results. 
     From the stock pre-preg resin/acetone solution, made with a resin concentration of 0.0068 g-resin/g-solution, dilutions of 1:10 to 1:500, were prepared. Using these solutions, standard resin-on-adhesive samples were prepared by dabbing 10 μl of solution onto the adhesive over a 0.75 cm diameter circular spot, an area of 0.44 cm 2 . These standard samples were used to obtain the calibration curve shown in  FIG. 11  from the peak intensity of the (1−Transmission) background corrected IR spectra at 3365 cm −1 . The top axis shows the diluted resin solution concentrations, which can be used as a guide for future calibrations. The bottom axis shows the resin surface concentration, determined from the resin solution concentration, the solution density (assumed to be the density of acetone, 0.791 g/cm 3 ), the total volume deposited (10 μl=0.01 cm 3 ) and the area (0.44 cm 2 ). For example, for a 1:50 dilution: 0.0068 g-resin/g-acetone·1/50·0.791 g-acetone/cm 3 ·0.01 cm 3 /0.44 cm 2 =2.4 μg-resin/cm 2 . The behavior appears linear although there is scatter from the nonuniformity of the standard samples. The line shown is a fit for the samples with resin surface concentrations from 1.2 μg/cm 2  to 12 μg/cm 2 . 
     From the linear fit shown in  FIG. 11 , the resin surface concentration for an unknown sample may be determined by inverting the fit. This inversion (surface resin concentration as a function of IR intensity at 3365 cm −1 ) is shown in  FIG. 12  together with upper and lower limits determined from the ±1σ variation of the linear fitting parameters, the slope and intercept. For this calibration: Resin concentration (g/cm 2 )=[(Intensity at 3365 cm −1 )−0.00164]/1345. The lower limit is: Resin concentration (g/cm 2 )=[(Intensity at 3365 cm −1 )−0.00232]/1445. The upper limit is: Resin concentration (g/cm 2 )=[(Intensity at 3365 cm −1 )−0.00095]/1245. We note that this calibration strictly applies only to the FTIR system used for these experiments and should be used with caution on other systems. Ideally, for each system used, a set of standard samples should be measured as shown in  FIG. 11 . 
     From the low concentration samples ( FIG. 11 , dilutions of 1:200, 1:300, and 1:500) a detection limit for the pre-preg resin on the adhesive measured by IR was estimated.  FIG. 13  shows background corrected 1-Transmission spectra for two 1:200 dilution standard samples (nominally 0.6 μg/cm 2 ) shown as dotted lines, and one 1:500 dilution sample (nominally 0.24 μg/cm 2 ) shown as dashed lines. These spectra were acquired with 1024 scans. No peak is observed for the 1:500 dilution sample. Similarly no peaks were observed for 1:300 dilution samples (not shown). For the 1:200 samples, one spectrum shows a clear peak while the other shows just the beginnings of a peak rising above the background. From these data and the fits shown in  FIG. 11 , we estimate the detection limit for this measurement to be about 1 μg-resin/cm 2 -adhesive. 
     Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. 
     While the present teachings have been illustrated with respect to one or more implementations, alterations and/or modifications can be made to the illustrated examples without departing from the spirit and scope of the appended claims. In addition, while a particular feature of the present teachings may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular function. Furthermore, to the extent that the terms “including,” “includes,” “having,” “has,” “with,” or variants thereof are used in either the detailed description and the claims, such terms are intended to be inclusive in a manner similar to the term “comprising.” Further, in the discussion and claims herein, the term “about” indicates that the value listed may be somewhat altered, as long as the alteration does not result in nonconformance of the process or structure to the intended purpose described herein. Finally, “exemplary” indicates the description is used as an example, rather than implying that it is an ideal. 
     It will be appreciated that variants of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompasses by the following claims.