Polyethylene-based porous oil sorbent with swellable pockets

Abstract

Freestanding porous polyethylene thin film, and a method for preparing a freestanding porous polyethylene thin film. The method includes dissolving polyethylene in an organic solvent to form a solution under reflux conditions; adding a swellable pocket forming agent to the solution and mixing the solution until the swellable pocket forming agent is well-dispersed therein; applying the well-dispersed solution onto a solid substrate through spin coating to form a thin film on the solid substrate; peeling the thin film off the solid substrate; and extracting the swellable pocket forming agent from the peeled thin film by washing the peeled thin film in water, thereby obtaining a freestanding porous polyethylene thin film with swellable pockets, macro-voids, and micropores. The freestanding porous polyethylene thin film can be used as an oil sorbent. The freestanding porous polyethylene thin film has about 500 to about 800 swellable cavities per cm.sup.2.

Claims

1. A method for preparing a freestanding porous polyethylene thin film, the method comprising: dissolving polyethylene in an organic solvent to form a solution under reflux conditions; adding a swellable pocket forming agent to the solution and mixing the solution until the swellable pocket forming agent is well-dispersed therein, thereby forming a well-dispersed solution; placing a solid substrate onto a spin coater chuck; applying the well-dispersed solution onto the solid substrate through spin coating to form a thin film on the solid substrate; collecting excess materials of the polyethylene and the organic solvent in a spin coated drain connected to a receiver; removing the solid substrate with the thin film formed thereon from the spin coater chuck; subjecting the formed thin film to post-heat; peeling the thin film off the solid substrate to obtain a peeled thin film; and extracting the swellable pocket forming agent from the peeled thin film by washing the peeled thin film in water, thereby obtaining a freestanding porous polyethylene thin film with swellable pockets, macro-voids, and micropores, wherein each of the swellable pockets are configured to swell twenty to thirty times a thickness of the freestanding porous polyethylene thin film when in contact with oil.

2. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the organic solvent is selected from the group consisting of p-xylene and an isomeric mixture of xylenes.

3. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the dissolving polyethylene step comprises dissolving the polyethylene and the organic solvent in a round-bottomed flask and connecting the round-bottomed flask to a reflux condenser to avoid loss of the organic solvent.

4. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the swellable pocket forming agent is selected from the group consisting of sodium chloride, mica, alumina, barium sulfate, barium carbonate, calcium sulfate, calcium oxide, calcium carbonate, diatomaceous earth, clay, talc, glass powder, kaolin, magnesium oxide, magnesium sulfate, magnesium carbonate, silica clay, silica, titanium oxide, zinc oxide, potassium chloride, calcium chloride, and a combination thereof; and wherein a size of the swellable pocket forming agent ranges from about 3 ?m to about 200 ?m.

5. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the solid substrate is selected from the group consisting of glass and metal.

6. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the freestanding porous polyethylene thin film is made of a virgin or recycled material selected from the group consisting of LDPE (low-density polyethylene), LLDPE (linear low-density polyethylene), HDPE (high-density polyethylene), UHMWPE (ultrahigh molecular weight polyethylene), and a combination thereof.

7. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the subjecting of the formed thin film to the post-heat occurs for about 5 seconds to about 25 minutes and is conducted at a temperature of about 25? C. to about 150? C.

8. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the swellable pocket forming agent is added to the solution in a ratio of the polyethylene to the swellable pocket forming agent of about 1:0 w/w % to about 1:2 w/w %.

9. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the macro-voids are formed by conducting the spin coating at a speed above about 600 rpm to obtain macro-void dimensions of between about 10 ?m and about 200 ?m.

10. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the freestanding porous polyethylene thin film is self-supporting, free of a support or a substrate or a wall surface.

11. The method for preparing a freestanding porous polyethylene thin film of claim 1, further comprising laminating the freestanding porous polyethylene thin film with a layer of superhydrophobic coating using a chemical vaporization technique or a physical vaporization technique to make the freestanding porous polyethylene thin film superoleophilic or superhydrophobic.

12. The method for preparing a freestanding porous polyethylene thin film of claim 1, further comprising laminating the freestanding porous polyethylene thin film with a nonwoven thin polypropylene fabric made up of fibers to provide support and further enhance sorption capacity of the freestanding porous polyethylene thin film.

13. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the freestanding porous polyethylene thin film is used as an oil sorbent.

14. The method for preparing a freestanding porous polyethylene thin film of claim 1, wherein the polyethylene comprises UHMWPE (ultrahigh molecular weight polyethylene) at 15 wt. % of the solution.

15. A freestanding porous polyethylene thin film prepared according to the method of claim 1, wherein the freestanding porous polyethylene thin film has about 500 to about 800 swellable pockets per cm.sup.2, wherein each of the swellable pockets can swell twenty to thirty times a thickness of the freestanding porous polyethylene thin film when in contact with oil.

16. The freestanding porous polyethylene thin film of claim 15, having a thickness of about 2 ?m to about 100 ?m, a tensile strength of about 3 MPa to about 60 MPa, and a porosity ranging from about 1% to about 75%.

17. The freestanding porous polyethylene thin film of claim 15, wherein the swellable pockets, the macro-voids, and the micropores have dimensions of about 150 ?m to about 200 ?m, about 30 ?m to about 100 ?m, and about 0.5 ?m to about 10 ?m, respectively.

18. The freestanding porous polyethylene thin film of claim 15, having an oil uptake capacity of about 70 g/g to about 160 g/g as measured immediately after taking out the freestanding porous polyethylene thin film from an oil bath.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1A-1B depict SEM images of polyethylene thin films with swellable pockets.

(2) In FIG. 1A, the porous thin film shows a swellable pocket from the top surface. In FIG. 1B, the porous thin film and the sponge-like swellable pocket show micropores.

(3) FIGS. 2A-2B depict SEM images of polyethylene thin films with swellable pockets and micropores. In FIG. 2A, a porous thin film with a swellable pocket from the top surface is shown. In FIG. 2B, the porous thin film and the swellable pocket with a microporous structure is shown.

(4) FIGS. 3A-3B depict SEM images of polyethylene thin film before (FIG. 3A) and after (FIG. 3B) heating.

(5) FIGS. 4A-4B depict 3D images of the porous thin film polymer showing micropores and swellable pockets using a profilometer. The porous thin film shows swellable pockets from the top surface (FIG. 4A) and the bottom surface (FIG. 4B)

(6) FIG. 5 is a schematic representation of a cross-sectional view of the porous thin film 2 with swellable pockets before peeling off from the substrate 1.

(7) FIG. 6 is a schematic representation of a cross-sectional view of a porous thin film 2 with micropores 5, macro-voids 6, and prefilled swellable pockets 3 with swellable pocket forming agent 4 on a solid substrate 1.

(8) FIG. 7 is a schematic representation of a cross-sectional view of a freestanding porous thin film 2 with micropores 5, macro-voids 6, and prefilled swellable pockets 3 with swellable pocket forming agent 4 separated from the solid substrate 1.

(9) FIG. 8 is a schematic representation of a cross-sectional view of a freestanding porous thin film 2 with micropores 5, macro-voids 6, and empty swellable pockets 7 with no swellable pocket forming agents.

(10) FIGS. 9A-9C are schematic representations of a porous thin film 2 with sponge-like swellable pockets in compressed form (FIG. 9A), after oil sorption (FIG. 9B), and after squeezing (FIG. 9C).

(11) FIG. 10 is a schematic representation of a thin film with swellable pocket laminated with a superhydrophobic coating.

(12) FIG. 11 is a schematic representation of thin film swellable pockets supported on a polypropylene support.

(13) FIG. 12 is a schematic representation of the steps of sealing of thin films into pouches.

(14) Similar reference characters denote corresponding features consistently throughout the attached drawings.

DETAILED DESCRIPTION

(15) The following definitions are provided for the purpose of understanding the present subject matter and for construing the appended patent claims.

Definitions

(16) Throughout the application, where compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings can also consist essentially of, or consist of, the recited components, and that the processes of the present teachings can also consist essentially of, or consist of, the recited process steps.

(17) It is noted that, as used in this specification and the appended claims, the singular forms a, an, and the include plural references unless the context clearly dictates otherwise.

(18) In the application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components. Further, it should be understood that elements and/or features of a composition or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present teachings, whether explicit or implicit herein.

(19) The use of the terms include, includes, including, have, has, or having should be generally understood as open-ended and non-limiting unless specifically stated otherwise.

(20) The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. In addition, where the use of the term about is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term about refers to a ?10% variation from the nominal value unless otherwise indicated or inferred.

(21) The term optional or optionally means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances in which it does not.

(22) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently described subject matter pertains.

(23) Where a range of values is provided, for example, concentration ranges, percentage ranges, or ratio ranges, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the described subject matter. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also encompassed within the described subject matter, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the described subject matter.

(24) Throughout the application, descriptions of various embodiments use comprising language. However, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language consisting essentially of or consisting of.

(25) For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

(26) The term PE (polyethylene) as used herein is intended to include LDPE (low-density polyethylene), LLDPE (linear low-density polyethylene), HDPE (high-density polyethylene), and UHMWPE (ultrahigh molecular weight polyethylene).

(27) The term free-standing thin film refers to a film that does not adhere to a support such as a substrate or a wall surface to maintain the film structure. It should be used independently without the support of any substrate or without forming a complex with the support. It should not be collapsed when used as a free-standing thin film.

(28) The term porous as used herein refers to a plurality of pores provided in a thin film. Further, the pores may or may not penetrate through the thin film. A porous thin film may have penetrating pores and non-penetrating pores.

(29) In one embodiment, the present subject matter relates to a method for preparing a freestanding porous polyethylene thin film comprising: dissolving polyethylene in an organic solvent to form a solution under reflux conditions; adding a swellable pocket forming agent to the solution and mixing the solution until the swellable pocket forming agent is well-dispersed therein, thereby forming a well-dispersed solution; placing a solid substrate onto a spin coater chuck; applying the well-dispersed solution onto the solid substrate through spin coating to form a thin film on the solid substrate; collecting excess materials of the polyethylene and the organic solvent in a spin coated drain connected to a receiver; removing the solid substrate with the thin film formed thereon from the spin coater chuck; subjecting the formed thin film to post-heat; peeling the thin film off the solid substrate to obtain a peeled thin film; and extracting the swellable pocket forming agent from the peeled thin film by washing the peeled thin film in water, thereby obtaining a freestanding porous polyethylene thin film with swellable pockets, macro-voids, and micropores.

(30) In an embodiment, the organic solvent can be selected from the group consisting of p-xylene and an isomeric mixture of xylenes.

(31) In another embodiment, the dissolving polyethylene step comprises dissolving the polyethylene and the organic solvent in a round-bottomed flask and connecting the round-bottomed flask to a reflux condenser to avoid loss of the organic solvent.

(32) In a further embodiment, the swellable pocket forming agent can be selected from the group consisting of sodium chloride, mica, alumina, barium sulfate, barium carbonate, calcium sulfate, calcium oxide, calcium carbonate, diatomaceous earth, clay, talc, glass powder, kaolin, magnesium oxide, magnesium sulfate, magnesium carbonate, silica clay, silica, titanium oxide, zinc oxide, potassium chloride, calcium chloride, and a combination thereof; and wherein a size of the swellable pocket forming agent can range from about 3 ?m to about 200 ?m.

(33) In an embodiment, the solid substrate can be selected from the group consisting of glass and metal.

(34) In some embodiments, the freestanding porous polyethylene thin film can be made of a virgin or recycled material selected from the group consisting of LDPE (low-density polyethylene), LLDPE (linear low-density polyethylene), HDPE (high-density polyethylene), UHMWPE (ultrahigh molecular weight polyethylene), and a combination thereof.

(35) In some embodiments, the formed thin film is subjected to the post-heat for about 5 seconds to about 25 minutes and which is conducted at a temperature of about 25? C. to about 150? C.

(36) In some embodiments, the swellable pocket forming agent can be added to the solution in a ratio of the polyethylene to the cavity forming agent of about 1:0 w/w % to about 1:2 w/w %.

(37) In some embodiments, the macro-voids can be formed by conducting the spin coating at a speed above about 600 rpm to obtain macro-void dimensions of between about 10 ?m and about 200 ?m.

(38) In some embodiments, the freestanding porous polyethylene thin film can be self-supporting, free of a support or a substrate or a wall surface.

(39) In some embodiments, the freestanding porous polyethylene thin film can be laminated with a layer of superhydrophobic coating using a chemical vaporization technique or a physical vaporization technique to make the freestanding porous polyethylene thin film superoleophilic or superhydrophobic.

(40) In some embodiments, the freestanding porous polyethylene thin film can be laminated with a nonwoven thin polypropylene fabric made up of fibers to provide support and further enhance sorption capacity of the freestanding porous polyethylene thin film.

(41) In some embodiments, the freestanding porous polyethylene thin film can be used as an oil sorbent.

(42) In other embodiments, the polyethylene can be UHMWPE (ultrahigh molecular weight polyethylene) at about 15 wt. % of the solution.

(43) In FIGS. 1A-1B, the porous thin film made of polyethylene with prefilled swellable pockets was prepared through spin coating. The peeled layer was washed in water to achieve empty swellable pockets. The porous thin film and the swellable pockets also showed micropores. The thickness of the thin film can range from about 2 ?m to about 100 ?m or, in certain embodiments, from about 2 ?m to about 20 ?m. The porous thin film can have an area ranging from about 1 cm.sup.2 to about 1296 cm.sup.2, or more, and a diameter of the film ranging from about 1 cm to about 36 cm, or more. The dimension of the swellable pocket forming agent can range from about 0.1 ?m to about 200 ?m or, in certain embodiments, from about 150 ?m to about 200 ?m. The height of the swellable pocket-forming agent can range from about 0.1 ?m to about 200 ?m or, in certain embodiments, from about 150 ?m to about 200 ?m. The length and/or breadth and/or depth(height) of the swellable pockets can range from about 0.1 ?m to about 200 ?m with an average dimension/diameter of about 150 Micropores can be through pores and can range from about 500 nm to about 10 ?m.

(44) In FIGS. 2A-2B, the porous thin film made of polyethylene with prefilled swellable pockets was prepared through spin coating. The peeled layer was washed in water to achieve empty swellable pockets.

(45) In FIGS. 3A-3B, a spin coating technique was used to prepare polyethylene thin films. Before post-heating, the structure of the polyethylene resembles flakes or petal-like structures. They are more porous but less strong. They cannot be reused as the tensile strength of these thin films is weak. They cannot be peeled-off easily. Upon heating the polyethylene molecules, the molecules become soft and form more intermolecular bonding between the polymer chains, resulting in a strong thin film. The heated thin film in FIG. 3B shows a porous structure with improved strength.

(46) In FIGS. 4A-4B, the porous thin film made of polyethylene with prefilled swellable pockets was prepared through spin coating. The peeled layer was washed in water to remove salt and to achieve empty swellable pockets.

(47) In FIG. 5, a porous thin film 2 made of polyolefin was prepared using the spin coating technique. The porous thin film 2 with prefilled swellable pockets 3 with swellable pocket forming agent 4 rests on a substrate 1. The porous thin film 2 on the substrate 1 prepared using the spin coating method with swellable pocket forming agent 4 is not yet peeled off. The solid substrate 1 can be a glass surface or metal surface. The glass substrate 1 is heated to a temperature ranging from about 130? C. to about 150? C. or a temperature up to the melting point of the polymer. After heating, the thin film 2 can be peeled off using a tweezer resulting in a freestanding thin film and can be independently held without any other support either on complex support or individual microporous support.

(48) In FIG. 6, a porous thin film made of polyolefin was prepared using the spin coating technique. The porous thin film 2 with prefilled swellable pockets 3 with swellable pocket forming agent 4 resting on a substrate 1 has a thickness ranging between about 2 ?m and about 100 ?m or, in certain embodiments, between about 2 ?m and about 20 ?m. Micropores 5 can be through pores and can range between about 0.5 ?m and about 10 ?m or, in certain embodiments, between about 500 nm and about 5 ?m. Macro-voids 6 are through pores and can range between about 10 ?m and about 200 ?m, or above, or in certain embodiments, between about 30 ?m and about 100 ?m. These macro-voids can be formed near the swellable pockets. They can be formed when the initial spin coat speed is high (above 600 rpm). If macro-voids are not desired, then the initial speed of the spin coat should be below about 500 rpm.

(49) In FIG. 7, a porous thin film made of polyolefin was prepared using the spin coating technique. The porous thin film 2 with prefilled swellable pockets 3 with swellable pocket forming agent 4 can be separated from a substrate 1. The thickness of the thin film 2 can range between about 2 ?m and about 100 ?m or, in certain embodiments, between about 2 ?m and about 20 ?m.

(50) In FIG. 8, a porous thin film 2 made of polyolefin was prepared using the spin coating technique. The porous thin film 2 with empty swellable pockets 7 was prepared through spin coating. The peeled layer was washed in water to achieve a thin film with empty swellable pockets.

(51) In FIG. 9A, the thin film 2 is in a packed state with compressed swellable pockets 10. Once it is put in oil, the micropores 5, compressed swellable pockets 10 can absorb oil 9 and expand to its maximum capacity and retain good volume of oil represented as swollen swellable pockets 11 as shown in FIG. 9B. When the oiled film is pressed or squeezed, the oil inside the swellable pockets 12 can be extracted and very minute amount of oil can be present inside the micropores 13 as shown in FIG. 9C. This film can be packed in a compressed form to occupy more films in a limited space. Further, this film can be reused for oil sorption for many a times without losing the structural integrity and structure collapse.

(52) In FIG. 10, the thin film 2 with swellable pockets is laminated with a nano hydrophobic layer 9 to make the thin film super oleophilic or superhydrophobic. The lamination or coating can be done with a chemical vaporization technique or physical vaporization technique. The thin film can be laminated with functionalization of any composition of interest as required for the application.

(53) In FIG. 11, a thin film is rested on a support made of nonwoven thin polypropylene fabric. This support enhances the strength, durability and recyclability. The pores of the nonwoven fabric is more than 1 mm, thus it does not block the properties of the thin film applications.

(54) In FIG. 12, a pouch is made of nonwoven polypropylene fabric which is heat sealed on three sides. Two or more porous thin films can be inserted into the pouch from the open side. After inserting the thin films, the pouch can be heat-sealed from the fourth side, connected to a thread which can be knotted and transformed into a bag. Then this bag can be easily used and dipped into the oil and later, oil can be squeezed to remove the oil and recycled. The bag can also be used for organics sorption from water.

EXAMPLES

Example 1

Preparation of HDPE Thin Film

(55) 3 g of HDPE is taken in a round-bottomed flask. 50 ml of p-xylene is added to the round-bottomed flask and allowed to stir. The reaction mixture is heated at 130? C. until a clear solution is achieved. Usually, the polymer is dissolved in 10-15 minutes. The round-bottomed flask is connected to a reflux condenser to avoid organic solvent loss. Add 6 g of sodium chloride size ranging between 150 ?m and 200 ?m. Allow the polymer reaction mixture to stir until a uniform dispersed solution is achieved.

(56) Simultaneously, a plain glass plate of size 5 cm?5 cm is heated to 120? C. Then it is placed on a customized spin coater chuck and the polymer reaction mixture is poured onto a hot glass surface and a lid of the spin coater chuck is closed to avoid organic solvent evaporation and exposure. The spin coater chuck is turned on and allowed to spin in three steps. A first step includes spinning at 600 rpm for 5 seconds, followed by a second step including spinning at 1000 rpm for 60 seconds, and a third step including spinning at 3000 rpm for 120 seconds. After the completion of spin coating, a white powdered layer is observed with no solvent in it. The solid substrate is removed from the spin coater chuck and placed in a hot air oven for 20 minutes at 130? C. Then the thin film is peeled off easily using a tweezer.

(57) The thin film is then washed in water for 5 minutes to remove the swellable pocket forming agent, sodium chloride, to obtain a macro-porous thin film layer. It is noted that a reaction hotplate-stirrer and the spin coater chuck are placed side-by-side to avoid solvent exposure to the environment. The whole setup is kept inside a fume hood. The spin coater drain is connected to a receiver. The thickness for the thin film achieved through this composition is 7 ?m. The strength obtained for this film is 4 MPa. The 3D images by profilometry shown in FIG. 4 are of this example. All the properties of this thin film are presented in Table 1, Example 2, which is further explained in Table 2. The SEM images shown in FIGS. 1-3 were prepared through this combination.

(58) TABLE-US-00001 TABLE 1 Tensile Strength comparison for different compositions of polyolefins and swellable pocket forming agents at optimized conditions. Polymer to swellable pocket Sample forming composition agent Polymer in (NaCl) Tensile Xylene ratio Thickness Strength Swellable Example [mg/ml] (w/w %) (?m) (MPa) pockets 1 HDPE 1:0 7 5 Absent [60 mg/ml] 2 HDPE 1:2 7 4 Present [60 mg/ml] 3 HDPE:UHMWPE 1:0 7 15 Absent (85:15) [30 mg/ml] 4 HDPE:UHMWPE 1:1 7 12 Present (85:15) [30 mg/ml] 5 HDPE:UHMWPE 1:2 7 10 Present (85:15) [30 mg/ml]

(59) TABLE-US-00002 TABLE 2 Porosity vs Strength comparison for HD porous thin film with swellable pockets (polymer: swellable pocket forming agent-1:2) (Example 2 in Table 1) .sup.1Thickness .sup.2Temperature Time Strength SN Porosity % (?m) ? C. min MPA 1 ~75 20 25 0 .sup.3ND 2 ~71 18 130 5 ND 3 ~66 16 130 10 1 4 ~60 14 130 15 2 5 ~30* 7 130 20 4 6 ~7 5 130 25 6 7 <1 5 135 5 6 .sup.1initial weight of the thin film was 7 mg. .sup.2Temperature should be close to the melting point of the polymer. For HD, Temp is 130? C. .sup.3Not determined-the polymer is in the form of petals or flakes and cannot be considered as a freestanding thin film, *Pore size ranges from 0.5 ?m to 2 ?m.

Example 2

Preparation of HDPE:UHMWPE Thin Film

(60) UHMWPE can be added to strengthen the sorbent. 1.275 g of HDPE and 0.225 g of UHMWPE are taken in a round-bottomed flask. 50 ml of isomeric mixture of xylenes is added to the round-bottomed flask and allowed to stir. The reaction mixture is heated at 130? C. until a clear solution is achieved. Usually, the polymer is dissolved in 10-15 minutes. The round-bottomed flask is connected to a reflux condenser to avoid organic solvent loss. Add 3 g of sodium chloride size ranging between 150 ?m and 200 ?m. Allow the polymer reaction mixture to stir until a uniform dispersed solution is achieved.

(61) Simultaneously, a plain glass plate of size 5 cm?5 cm is heated to 120? C. Then it is placed on the customized spin coater chuck and the polymer reaction mixture is poured onto the hot solid surface and the lid of the spin coater is closed to avoid solvent evaporation and exposure. The spin coater is turned on and allowed to spin in three steps. The first step includes spinning at 600 rpm for 5 seconds, followed by the second step including spinning at 1000 rpm for 60 seconds, and the third step including spinning at 3000 rpm for 120 seconds. After the completion of spin coating, a white powdered layer is observed with no solvent in it. The solid substrate is removed from the chuck and placed in a hot air oven for 20 minutes at 130? C. Then the thin film is peeled off easily using a tweezer.

(62) Wash the film in water for 5 minutes to remove the swellable pocket forming agent, sodium chloride, to obtain a macro-porous thin film layer. The reaction hotplate-stirrer and spin coater are placed side-by-side to avoid solvent exposure to the environment. The whole setup is kept inside the fume hood. The spin coater drain is connected to a receiver and excess polymer and xylene is collected. The thickness for the thin film achieved through this composition is 7 ?m. The strength obtained for this film is 10 MPa. HDPE and UHMWPE were taken according to the above formulation and thin films on a glass substrate were prepared. All the properties of this thin film are presented in Table 1, Example 5, which is further explained in Table 3.

(63) TABLE-US-00003 TABLE 3 Porosity vs Strength comparison for HDPE-UHMWPE porous thin film with swellable pockets (polymer: swellable pocket forming agent-1:2) (Example 5 in Table 1) .sup.1Thickness .sup.2Temperature Time Strength SN Porosity % (?m) ? C. min MPA 1 ~75 20 25 0 .sup.3ND 2 ~71 18 130 5 ND 3 ~66 16 130 10 1 4 ~60 14 130 15 2 5 ~30* 7 130 20 10 6 ~7 5 130 25 12 7 <1 5 135 5 13 .sup.1initial weight of the thin film was 7 mg. .sup.2Temperature should be close to the melting point of the polymer. For HD, Temp is 130? C. .sup.3Not determined-the polymer is in the form of petals or flakes and cannot be considered as a freestanding thin film, *Pore size ranges from 0.5 ?m to 2 ?m.

Example 3

UHMWPE Usage

(64) UHMWPE (ultra-high molecular weight polyethylene) is added to strengthen the thin films. When it is added at 15 wt %, the strength is enhanced by three times. As UHMWPE is a PE, it does not create a compatibility problem when used with HDPE or other PEs. Instead, on the addition of UHMWPE, the viscosity of the solution is increased. Example 3-5 in Table 1 and Tables 3 to 10 reflect the results using UHMWPE.

(65) TABLE-US-00004 TABLE 4 Porosity vs Strength comparison for HDPE-UHMWPE porous thin film with no swellable pockets (polymer: swellable pocket forming agent-1:0) (Example 3 in Table 1) .sup.1Thickness .sup.2Temperature Time Strength SN Porosity % (?m) ? C. min MPA 1 ~75 20 25 0 .sup.3ND 2 ~71 18 130 5 ND 3 ~66 16 130 10 1 4 ~60 14 130 15 5 5 ~30* 7 130 20 15 6 ~7 5 130 25 26 7 <1 5 135 5 27 .sup.1initial weight of the thin film was 7 mg. .sup.2Temperature should be close to the melting point of the polymer. For HD, Temp is 130? C. .sup.3Not determined-the polymer is in the form of petals or flakes and cannot be considered as a freestanding thin film, *Pore size ranges from 0.5 ?m to 2 ?m.

(66) TABLE-US-00005 TABLE 5 Porosity vs Strength comparison for HDPE-UHMWPE porous thin film with swellable pockets (polymer: swellable pocket forming agent-1:1) (Example 4 in Table 1) .sup.1Thickness .sup.2Temperature Time Strength SN Porosity % (?m) ? C. min MPA 1 ~75 20 25 0 .sup.3ND 2 ~71 18 130 5 1 3 ~66 16 130 10 2 4 ~60 14 130 15 6 5 ~30* 7 130 20 12 6 ~7 5 130 25 14 7 <1 5 135 5 16 .sup.1initial weight of the thin film was 7 mg. .sup.2Temperature should be close to the melting point of the polymer. For HD, Temp is 130? C. .sup.3Not determined-the polymer is in the form of petals or flakes and cannot be considered as a freestanding thin film, *Pore size ranges from 0.5 ?m to 2 ?m

(67) TABLE-US-00006 TABLE 6 Retention capacity of Example 5 (HDPE-UHMWPE) thin film using engine oil. Dripping time Oil uptake S.N. (min) capacity.sup.1 (g/g) 1 0 160 2 0.5 130 3 1 110 4 2 108 5 5 105 6 15 105 .sup.1Oil uptake capacity with an error of ?10%

(68) TABLE-US-00007 TABLE 7 Saturation capacity profile of Example 5 (HDPE-UHMWPE) thin film using engine oil Oil Oil uptake uptake Saturation capacity* capacity** S.N. time (min) (g/g) (g/g) 1 0.5 70 55 2 1 110 80 3 2 160 105 4 5 160 105 5 15 160 105 *Oil uptake measured immediately after taking out the film from an oil bath **Oil uptake measured after equilibrium is reached (after dripping for 5 mins)

(69) TABLE-US-00008 TABLE 8 Comparison of oil uptake capacity.sup.1 using Example 5 sorbent with commercial sorbents using engine oil. Sorbent 3M Chemtex BP9W S.N. (g/g) HP-255 (g/g) (g/g) 1* 160 27 22 2** 105 23 17 .sup.1Oil uptake capacity with an error of ?10% *Oil uptake measured immediately after taking out the film from an oil bath **Oil uptake measured after equilibrium is reached (after dripping for 5 mins)

(70) TABLE-US-00009 TABLE 9 Comparison with different oils and liquids using Example 5 sorbent. Uptake Uptake capacity capacity Oil (g/g).sup.1 (g/g).sup.2 Toluene 40 25 Sunflower Oil 110 65 Paraffin Oil 90 45 Synthetic Oil 130 85 Engine Oil 160 105 .sup.1uptake capacity immediately after oil sorption; .sup.2uptake capacity after 5 minutes dripping.

(71) TABLE-US-00010 TABLE 10 Oil water separation efficiency using Example 5 sorbent. Oil in water SN (ppm) Efficiency % 1 1000 40 2 800 50 3 600 66 4 500 80 5 400 100 6 200 100 7 100 100 8 1 100

Example 4

Oil Sorption Studies

(72) The oil sorption studies including dripping kinetics and saturation kinetics and comparison with commercial sorbents as shown in Table 6, 7, and 8 respectively were done using the Example 5. Then these thin films were subjected to post-heat at varying temperatures. We have measured tensile strength and porosity for these samples that can be used as freestanding thin films. These values are mentioned in Tables 1-6.

(73) TABLE-US-00011 TABLE 11 Porosity vs Strength comparison for HD porous thin film with no swellable pockets (polymer: swellable pocket forming agent-1:0) (Example 1 in Table 1) .sup.1Thickness .sup.2Temperature Time Strength SN Porosity % (?m) ? C. min MPA 1 ~75 20 25 0 .sup.3ND 2 ~71 18 130 5 ND 3 ~66 16 130 10 1 4 ~60 14 130 15 2 5 ~30* 7 130 20 5 6 ~7 5 130 25 9 7 <1 5 135 5 10 .sup.1initial weight of the thin film was 7 mg. .sup.2Temperature should be close to the melting point of the polymer. For HD, Temp is 130? C. .sup.3Not determined-the polymer is in the form of petals or flakes and cannot be considered as a freestanding thin film, *Pore size ranges from 0.5 ?m to 2 ?m.

(74) Dripping kinetics is the amount of oil dripped from the thin film with respect to time. When a thin film is placed or dipped in oil, it absorbs oil till it reaches saturation. After it reaches equilibrium, the thin film is taken out and loosely connected oil is allowed to drain from it. Initially, oil will drip more and as time passes, the dripping decreases, and after some time some oil is retain by the film and oil is not dripped. This is termed as retention capacity of the thin film. The as-prepared thin film sorbent reaches its equilibrium uptake value after 5 minutes of dripping (i.e., after 5 minutes there will be no more dripping of oil from the sorbent).

(75) Saturation kinetics is the time taken by the thin film to reach a saturation point, whereafter the oil cannot be absorbed anymore. In short, it is the maximum capacity of the oil absorbed by the thin film with respect to time. The as-prepared thin film sorbent reaches its saturation value within 5 minutes of sorption. Comparison of the present as-prepared oil sorbent film with commercial sorbents was conducted. An area of 16 cm.sup.2 of 3 M and Chemtex commercial sorbents were cut and were compared with an area of 16 cm.sup.2 size of thin film as shown in Table 8. The equilibrium oil uptake value of the present porous sorbent was found to be 90 g/g, which is much higher than the commercial sorbent pads made of nonwoven polypropylene fabric. Lastly, different oil and organic solvents were used to measure the uptake capacity of the present sorbent and reported in Table 9.

Example 5

Separation Efficiency

(76) The sorbent film of 16 cm.sup.2 and a thickness of 7 ?m was used to measure oil water separation efficiency. Initially, the film was installed on a sintered glass filtration unit and a solution of 1000 ppm oil suspended in water was allowed to pass through the filtration unit. The results, reported in Table 10, were of Example 5. The film had a 100% oil water separation efficiency with a maximum capacity of 400 ppm per cm.sup.2 of sorbent film.

(77) It is to be understood that the present processes, compositions, and methods are not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.