Areas of open and inland waters and shorelines are with increasing frequency being polluted by the spillage of oil. One major approach to alleviating this problem has been the development of apparatus and methods for preventing the spreading of spilled oil by confining it to the area near its discharge. This facilitates removal, by causing the oil to concentrate in thicker layers on the surface of the water.

Containment of spilled oil employs commercially available floating booms such as exemplified in the oil collection boom of U.S. patent No. 3,679,058 (Smith) or sorbent barriers such as that described in United States patent No. 3,739,913 (Bogosian) .

Such containment techniques are not fully effective, as water currents, waves and wind conditions often lead to the escape from the containment region of oil which forms an outwardly spreading film that diminishes from a few

millimeters down to fractions of a micron (0.001 mm) in thickness as it moves towards the shoreline, where it can present a serious ecological threat to sensitive areas, such as fish-hatcheries, wildlife preserves, harbours and beaches. A number of sorbent materials have been proposed or made commercially available for the purpose of picking up oil which has escaped from containment booms and for protecting shorelines. These range from natural products, such as straw or sawdust, to synthetics ^• such as polypropylene or polyurethane foam, or relatively thick (5 mm or greater) mats, sheets or rolls of melt-spun and fabric-stitched oleophilic polymers. Examples of the latter include 3M™ Type 156 pads and ALSORB™ sheets or rolls.

Fibrous synthetic sorbent sheets of the kind presently in use have high sorption capacities, but tend to be considerably more expensive than natural or inorganic products. Their utilization has been restricted to smaller spills in sheltered waters or to recover oil whose access by skimmers or other mechanical means is difficult, such as under docks etc. They can as well be of value for use and re-use to pick up oil within containment areas, where the high thickness of oil enables economical use of their full capacity. Re-useability of such materials, by squeezing oil from the porous interior, is stated to be a major advantage. As a practical matter, however, reusability may be an economic necessity because of the price of such materials. Further, reusability requires apparatus and facilities for extracting and collecting the oil from the used sorbent.

Known oil sorbent materials have not adequately met the need for a relatively inexpensive sorbent which exhibits a high pick-up ratio for oil, which can be conveniently stored in quantity in a relatively small space, and which can be readily deployed onto sensitive areas to protect them against approaching oil slicks. The minimum thickness of conventional synthetic sorbent materials in the form of sheets or rolls of non-woven polymer fibres is around 5mm, which imposes a limit on the quantity of such sorbent which can .be stored in a given space. As discussed in greater detail below, it is desirable that there be available for use considerably thinner sorbent materials which nevertheless exhibit an adequate affinity for oil, measured by the pick¬ up ratio, to make it practical to keep substantial amounts of sorbent in storage at the ready for use in the event of an emergency. A principal desirable property not exhibited by presently available sorbents is the combination of a high storage density with a sufficiently high pick-up ratio. By "pick-up ratio" is meant the mass of oil which adheres to a given dry mass of sorbent, in use, symbolized hereinafter as

Moreover, particularly on application to very thin water-borne oil films, sorbents in the form of mats or pads of synthetic fibre are subject to varying degrees of undesirable water pickup as a portion of these thicker materials rides below the oil surface and in the water.

I have discovered that relatively thin flexible sheets of oleophilic, hydrophobic substrates such as polyethylene film may be used as the basis for effective and commerically advantageous sorbent media, particularly for deployment on sensitive areas as a first line of defence against approaching oil slicks, but also, in particular, embodiments of the invention, for early assistance in the containment of oil at or near the source of a spill. Such sorbent media are sufficiently inexpensive that disposal of the oil-charged medium after use, as by incineration, is economically practical, by contrast with the more expensive synthetic sorbent media currently available. However, the sorbent media according to the invention may alternatively be re-used following extraction of absorbed and adsorbed oil. Too, having no fibrous structure and being made of thinbuoyant material, sorbent media according to the present invention are inherently free of water pickup.

The underlying principle of my novel sorbent media is that the degree of sorption of oil on an oleophilic surface is a function of the surface area and configuration of such media. Use of the thinnest substrate allowing sufficient mechanical strength results in the greatest value of m ₀ /m., and hence economy, for such a sorbent medium. This is fundamentally different from the fibrous web-type sorbents which, in many applications, have a substantial unused capacity for oil, as illustrated below.

BRIEF SUMMARY OF THE INVENTION

It is an object of the invention to provide sorbent media which can be stored in quantity in a relatively small storage space for ready deployment over a given area of oil- contaminated water surface, or a given area of shoreline water or land area to be protected from encroaching water- borne oil spills, and which will substantially reduce the risk and extent of contamination of such areas. In particular, it is an object to provide a film-form sorbent medium which can be stored on rolls at storage stations in sensitive areas and readily deployed by reeling off one or more layers of sorbent as needed for coverage.

It is a further object of the invention to provide sheet-like sorbent media having an oil-pickup capacity per unit area more closely matched to the thickness of surface oil to be removed, than prior known sheet-form oil sorbent media.

With a view to achieving these objects, the invention is- in one aspect a thin, sheet-like sorbent material for collecting contaminating oil from the surface of open water and for protecting shoreline water or land areas from approaching oil slicks by extending at least one layer thereof onto the oil-contaminated water surface or area to be protected, comprising a flexible film of material, at least one of whose two principal surfaces is oleophilic and hydrophobic.

In other embodiments, there is provided a thin, sheet-like sorbent material comprising a pair of oleophilic, hydrophobic films joined together along sealing seams defining interior pockets having apertures therethrough to admit migration of contaminating oil into the pockets, or a pair of oleophilic hydrophobic films sealingly laminated together with at least one of said films having been embossed to form a plurality of cells, each such cell having apertures through opposite surfaces thereof to receive contaminating oil. Having an enhanced pick-up ratio by virtue of multiple oleophilic layers and oil-receiving pockets within their structure, such embodiments are adapted for use and deployment at or near the source of spillage (e.g. tankers and floating drill platforms), where oil thickness on the water is greater than on areas of open water remote from the spill. BRIEF DESCRIPTION OF THE DRAWINGS

The invention and other objects and advantages thereof will be more fully understood with reference to the following drawings in which:

Figure 1 is a schematic sectional view of a creased thin sorbent material according to one embodiment of the invention, illustrating the tendency of oil to collect at concave portions of an oleophilic, hydrophobic surface; Figure 2 is a schematic sectional view as in Figure

1, illustrating the pattern of collection at concave surface

portions for a higher viscosity oil than that illustrated in connection with Figure 1;

Figure 3 is a schematic drawing illustrating the deployment of a film-form sorbent according to any of the embodiments of the invention from a roll dispenser on a small boat to protect a sensitive area threatened by an approaching oil slick;

Figure 4 is a perspective view of a portion of a sorbent material according to one embodiment of the invention;

Figure 5 is a plan view of one of the formed pockets in the sorbent material of Figure 4;

Figure 6 is a sectional view along the line 6-6 of Figure 5; Figure 7 is a schematic view of the pocket of sorbent material of Figure 5 following entrapment of oil in the pocket;

Figure 8 is a sectional view along the line 8-8 of Figure 7; Figure 9 is a top perspective view of a double-film sorbent medium made according to a further embodiment of the invention;

Figure 10 is a cross-sectional view of the sorbent medium embodiment of Figure 9; and Figure 11 is a perspective view of a portion of a sheet of sorbent material according to a further embodiment the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the embodiments of this invention, there will be disclosed several arrangements for film-based, sheet-like sorbent materials according to the invention and their measured essential properties, compared with a prior art sorbent, namely 3M Type 151 and Type 156 pads. These are, respectively, 3/16" (0.5 cm) and 3/8" (l cm) thick fabric consisting of non-woven synthetic polyolefin fibres containing small voids throughout.

EXPERIMENTAL PROCEDURE

A small specimen (about 5cm x 6cm) of each sorbent material tested, having a measured area equal to'A, cm ² was first weighed dry (m, grams) and was then (with the exception of specimen S ₀ ) laid on one face on the surface of a bath of 10W40 motor oil (density = 0.88 gm/cm ³ ) and allowed to float on the oil until it was seen that the top surface of the specimen was completely covered by oil. Specimen S ₀ , being an unperforated integral film, total immersion in oil was required, as there are no through-film passages for migration of oil between the principal surfaces for this particular specimen.

The specimen was then removed by one corner or end and allowed to hang until dripping stopped, then weighed to give the combined weight of oil pick-up plus sorbent weight, (mo+m_) g. For each specimen, the following parameters were then calculated:

i) the aforementioned oil pick-up ratio iri _o / -, which provides a dimensionless measure of the inherent affinity for oil of the sorbent tested; ii) the ratio A,/m„ [cm ² /g], the surface area presented by a unit mass of dry sorbent material; iii) the ratio m ₀ /A ₅ [g/cm ² ], the mass of oil taken up by unit area of dry sorbent material; and iv) the quantity (m _o /A _B )/0.088 [mm]. This quantity referred to hereinafter as the "related oil thickness" characterizing the particular sorbent, is a measure of the maximum theoretical thickness of film of 10W40 oil (density = 0.88g/cm ³ ) which can be fully taken up by a sorbent sheet exposed to the oil film.

The experimental results are set out below in Table

I, following which the various sorbent materials are identified and described. "S" refers to a sorbent material comprising a single film of material and "D" refers to a double-film sorbent material. Each data entry represents the average of three experimental measurements.

TABLE I

"Related Oil thickness"

Sorbent fm-/A.Ϊ/0.088

3M Type

151 9.90 50.0cm ² /g 0.196g/cm ² 2.23 mm

3M Type 156 8.10 26.0 0.312 3.54

5.70 1,090 5.24x10 ^" 0.059

S_ 6.80 1,090 6.26x10 ^" 0.071

6.50 1,090 5.98x10 ^" 0.067

7.70 1,000 7.70x10 ^" 0.087

D ₁ 6.20 543 1.14x10 ^" 0.129

16.2 543 2.98x10 ^" 0.338

32.7 500 6.54X10 ^" 0.743

D« 35.6 500 7.12x10 ^" 0.809

24.2 75.0 0.323 3.67

16.4 147 0.060 1.061

S ₀ , Si, S ₂ , and S ₃ were specimens of flexible polyethylene film of a thickness of about .01mm (10 microns) and a density of about 0.92gm/cm ³ . S ₀ , unlike all other samples, was fully immersed in oil prior to effecting the experimental measurements, to provide a measure of the oil- pickup properties of polyethylene film not subjected to any deformation or breaks in its surface.

Si was made of the same material as S ₀ , but randomly pierced with a needle, with an average of about three pierces per cm ² of sorbent surface. Sample S ₂ also was provided with apertures through the film to permit the passage of oil, but in the form of 1cm slits, with an average of four such slits per cm ² of surface. Oil penetrating from the bottom of floated samples S _x and S ₂ was seen to spread over and fully cover the top surface of each specimen.

Comparison of the pick-up ratios of Si and S ₂ , 6.80 and 6.50 respectively, with the value of 5.70 for the "untreated" polyethylene film substrate in repeated experiments suggests that pierces and slits not only serve to allow the passage of oil from one major surface through to and across the other major surface, but also that additional oil collects at the puncture or slit discontinuities in the film.

The effect of surface texture irregularities in enhancing the degree of sorption of oil is illustrated by the still higher value of πio/ir = 7.70 for S ₃ , a polyethylene film slit like S ₂ but also formed with "creases" made by holding the specimen in a twisted configuration for 48 hours at a tension less than that sufficient to induce any appreciable cold flowing of the plastic.

Figures 1 and 2 represent the pooling of oil at the concave surfaces in cross-sectional schematic views of such a creased film. A portion of a creased film such as S ₃ is indicated at 10 in 'Figures 1 and 2. For simplicity of representation, the apertures through film 10 are not shown. Indicated at 12a in Figure 1 is the film-forming contour of

a low-viscosity oil adsorbed to the surface of film 10. Indicated at 12b in Figure 2 is the thickness pattern of a higher-viscosity oil adsorbed to the surface of film 10. "bridging" zones of concave curvature where the adsorbed oil tends to collect in thicker pools are indicated at 13a in Figure 1 and at 13b in Figure 2. As noted above, the piercing of flat or creased films itself creates discontinuities. The annular concave surfaces around the pierced holes on one side of the film also act as bridging zones to augment the adherence of oil at such sites.

The practical advantages of a single-film substrate according to one embodiment of the invention may be seen by comparing the entries in Table I for sorbent S ₃ with those for 3M Type 151 and considering the use of either to deal with an oil slick of thickness one micron (0.001mm). The "relative oil thickness" of the absorbent-pad 3M material is more than 2,000 times as great as the oil slick, while that of the S ₃ is only about nine times as great. For a given area of sorbent material, the weight of 3M material is about 20 times that of S ₃ , so that the economic advantage of employing the film-form material is apparent.

3M Type 156 sorbent sheeting, which is twice as thick as Type 151, is available in standard rolls of 32" diameter and 36" width. Polyethylene film of the type used in specimens S ₀ tp S ₃ is available in 10" diameter by 25" width standard rolls. By a straightforward geometric calculation it may be seen that one cubic meter of storage space will accommodate only about 90m ² of the 3M sorbent and about 72,000 m ² of the film-form substrate, a storage density greater by a factor of about 800. This provides a clear advantage for the ready storage and deployment of the film- form sorbent. Thus, for example,a beachfront area could be provided with positioned roll dispensers to lay out one or more layers of sorbent according to the invention. With such a product, a 25" wide, 50 pound roll would cover approximately 25,000 square feet of area. Upon notice of an

approaching oil slick, a small boat or rubber raft could participate in protecting a sensitive area by reeling off a sorbent of the type S ₃ in front of the sensitive area, as a relatively inexpensive first line of defence. Figure 3 illustrates in schematic fashion the deployment in a sheltered cove of film-form sorbent material by a small two-man boat 18. The sorbent 16 can simply be reeled off a roll dispenser 20 in multiple rows as appropriate to the local topography and prevailing conditions.

The aforementioned high storage density (25,000 sq. ft. per "standard" roll) of film-form sorbents also makes it a practical application for such materials to be stored on oil tankers, floating oil rigs or other potential sources of oil spillage on open water for rapid deployment about or onto the spilling oil to reduce spreading at and near the source, i.e. for preliminary assistance in containment until a conventional boom-type containment system can be put in place. Alternatively, rows of film-form sorbent according to the invention could be dispensed from payout means installed on a helicopter positioned over forming oil slicks, near such sources of spillage as floating oil rigs, and laid down from above the spill source. It will be appreciated by those of ordinary skill in the art that any of a number of thin sheet-like sorbent materials having oleophilic and hydrophobic properties could be used to take advantage of the large value of nio/m,, characterizing such materials. Examples S _x to S ₃ relate to films of oleophilic polymers such as polyethylene having a density less than that of water, to float on the surface of the oil-contaminated water. Other potential variations and their applications contemplated are as follows:

Paper treated on one side to have an oleophilic and hydrophobic upper surface could be used as a sorption substrate by application, for example, to a beach surface

threatened with an approaching oil spill, with its oleophilic, hydrophobic surface facing upwardly and the hydrophilic paper surface at the bottom. The paper will then tend to absorb water in use when the substrate is exposed to oil-contaminated water washing onto shore, and the added weight of the substrate by absorption of water will tend to hold the sorbent in place during adsorption of oil by the oleophilic upper surface.

In a different class of embodiments of the invention two or more flexible oleophilic and hydrophobic films are joined together along portions of their facing principal surfaces to form separate pockets or domes, and suitable apertures are made through the films into the pockets to admit oil. Specimens D^ and D ₂ were formed by layering two films of the same polyethylene as specimen S ₀ together and heat sealing the films along perpendicular sealing seams to form a rectangular matrix of 40x50 mm pockets. In the case of D _1# several small slits were made on both sides of each such pocket, whereas in D ₂ , the only apertures into each pocket was a pair of offset circular near-central holes of diameter 3/16 through respective opposite surfaces of each pocket.

Specimen D ₂ is illustrated in Figures 4 to 8. Figure 4 shows a perspective view of this sorbent material with the two polyethylene films 22a and 22b formed into a matrix of individual pockets such as 23 by sealing seams 24. One such pocket of a D ₂ specimen is illustrated prior to use in Figures 5 and 6 and after pickup of oil 10 in Figures 7 and 8.

As best seen in Figure 5 and the cross-sectional view of Figure 6, pocket 23 has two offset central holes 25a and 25b through respective upper and lower film surfaces 22a and 22b. It was observed that the average value of the oil pick-up ratio m _o /r for D ₂ (16.2) was about three times as

great as the corresponding slit specimen Dj (6.20). From visual observation, it appears that when specimen D ₂ is laid on the oil surface the immediate contact of oil with the exposed portion of the interior surface of the upper film 25a and the olephilic interaction at that site facilitates the migration of oil along the interior film faces, where it is trapped in the pocket, as seen in Figure 7 and the sectional view of Figure 8. By having all pockets, centrally pierced, collected oil stays in the pockets below the aperture when the sorbent sheet is drawn from the treated area after use.

As illustrated in Figures 9 and 10, a further modification to the sorbent media Dj _. or D ₂ which has been seen to improve the oil-pickup ratio is achieved by forming the pockets 23 between the sealing seams 24 so that at least one of the two lateral film surfaces of each pocket is stretched or deformed away from the plane of the sorbent sheet so that it yields upon entry of oil into the pocket to form a "dome". In the perspective and sectional views of Figures 9 and 10, respectively, the dome-forming film is indicated as 22'a and the base-forming film as 22b. Where films 22'a and 22b are made of a polyolefin polymer having a density less than that of water, oil will tend to enter the pockets through offset central apertures 25a and 25b like those of the embodiment of Figures 4 to 8 and spread along the interior film surfaces, as illustrated by arrows A and B.

The dome-forming film 22'a can be made, for example, by creasing one film prior to joining the two films together along sealing seams. Specimens D ₃ and D ₄ are double- film layer sorbents of the same polyethylene material as O and D ₂ but in each of D ₃ and D ₄ one of the two component films was creased before fusing the films along seam lines into pockets. D ₃ and D ₄ differ from each other in that the apertures through the pocket faces are a plurality of small slits for D ₃ and a central pair of offset holes in the case

of D ₄ . The average oil pick-up ratio for D3 and D4 were seen to be 32.7 and 35.6, respectively.

Comparison of specimen D ₂ and the "doming" specimens D ₄ with specimens S ₀ to S ₃ indicate that the use of a double layer of film with suitable formation of pockets and apertures gives rise to an oil retention which is more than double that of the single layer films of like materials.

The "related oil thickness" for the single film embodiments tested ranges from about 0.05 to 0.09 mm and for the double film from about 0.1 to about 0.8 mm, still much less than the 2.23mm of the 3M Type 151 sorbent, but affording a useful and economical substrate for dealing with heavier oil films, particularly on shoreline waters where greater physical rigidity of sorbents is required. Increasing the interior of volume capacity of pockets in the double-film sorbent for oil can be achieved not only by forming at least one of the films to dome outwardly in use, but alternatively by forming two flat, specular oleophilic hydrophobic films into pockets containing a small amount of granular or fibrous "spacing" material within each of the pockets to maintain separation of the films across the inner pocket faces and facilitate migration of oil into the pockets through apertures in the constituent films. Advantageously the aforementioned granular or fibrous spacing material may include any of a number of known substances active in the degradation of oil, such as INOPOL EPA 22 produced by Elf Aquitane, oil-decomposing bacteria, etc. and enzymes which actively promote the degradation by bacteria already present of contaminants such as dioxins.

A further method of preparing sheet-like sorbent materials according to the invention is to form a "cellular" material of two oleophilic and hydrophobic films and provide central apertures through opposite faces of each cell, to admit and capture oil.

Air-cellular cushioning material such as Induspak CELLUL AIR ™ and Sealed Air of Canada Ltd.'s POLYCAP ™ bubble sheets are typically made of flexible plastics having the requisite oleophilic hydrophobic characteristics essential to oil sorbency.

Specimens D ₅ and D ₆ were samples of the CELLUL AIR material having 1-1/8" and 3/8" diameter bubbles, respectively, which were centrally pierced through each bubble and its subtending backing film. Figure 11 illustrates in perspective view at a portion of material 26 of the kind exemplified by specimens D ₅ or D ₆ , comprising a flat film layer 28a sealed to an embossed film layer 28b presenting a number of embossed portions 29 and associated cavity-forming regions 30. Central holes 31 and 32 are provided through the top surface of embossed portion 28b and the underlying portion of film layer 28a, respectively. ien these materials were placed in oil in the course of the above-described experimental testing, it was observed that oil tended to enter and restore the shape of the pierced bubbles even when these were physically collapsed prior to placement of the specimen in oil. Sheets of such materials, preparatory to use, can therefore be stored in rolls with the bubbles partially or nearly completely collapsed, so that a high storage density relative to conventional fibre mat sorbents is still achieved.

Smaller values of A./m _s for these materials compared with specimens D. to D ₄ is reflective of the greater film thickness and areal density of the plastic used in the air-cellular cushioning material which is intended to impart packing strength. Specifically, the bubble-form film of Specimen D ₅ was of thickness 0.02mm and the backing (unembossed) film was of thickness 0.045mm. For a given area of sorbent material, the weight of D ₅ is about 13 times that of S ₃ , but the "related- oil thickness" is 42 times as great. Thus for thicker oil films the "cellular" sorbent medium is to be preferred. Fabrication of such materials with thinner

film than used in commercial bubble sheet packing would be expected to lower the weight per unit of substrate without substantially lowering its oil pick-up capacity.

As seen from Table I, the "related oil thickness" of Specimen D ₅ , 3.67mm, is comparable to that of the 3M Type 156 sorbent and corresponds to the thickness of oil on water very near to the source of a substantial spill or from a tanker or floating oil rig. Taken with the higher storage density of such material compared to bulky fibre-sheets or rolls, rolls of the double-film sorbent substrates having pierced cells therein, according to this last-discussed specific embodiment of the invention, are particularly adapted for storage on potential sources of oil spills, from which they could immediately be deployed about or onto spilling oil in the event of a mishap pending arrival or setting up of conventional boom containment arrangements, to serve as a useful first line of prevention near or at the source of the oil spill