Self healing salt water barrier

FIELD OF THE INVENTION

0001The present invention is directed to methods and articles of manufacture useful as waterproofing membranes for waterproofing surfaces against the penetration of high conductivity salt- containing water, e.g., bay water, groundwater, marsh water, brackish water, ocean water, mining waste water, such as in the formation of waterproofed construction areas subjected to contact with high conductivity waters such as lagoons, hazardous or toxic waste containment areas, subterranean foundation surfaces and the like. More particularly, the present invention is directed to salt-water waterproofing articles of manufacture formed by confining a partially cross-linked polyacrylamide/partially neutralized polyacrylic acid copolymer in a mat. Alternatively, the copolymer can be forced into the non-woven fabric mat after formation of the mat or produced directly in the structure via polymerization or other processes.

BACKGROUND OF THE INVENTION AND PRIOR ART

0002Various polymers, swellable clays, and multi-layer articles of manufacture have been applied to the surface of soil to provide a waterproofing layer to prevent the penetration of water and/or hazardous or toxic materials into the earth, and to provide lagoons, ponds and other water-containment areas. Water-swellable clays, such as bentonite, have been applied directly to the soil surface and impacted in place, as disclosed in this assignee's prior <patcit id="pcit0001" dnum="US3986365A"><text>U.S. Pat. No. 3,986,365</text></patcit>. In addition, many different multi-layered articles of manufacture containing a water-swellable clay, such as sodium bentonite, have been manufactured by securing the water-swellable clay to major interior surfaces of flexible sheet materials, e.g., Clem <patcit id="pcit0002" dnum="US4501788A"><text>U.S. Pat. No. 4,501,788</text></patcit>, for application to the soil surface in abutting or overlapping relation to adjoining multi-layered articles. Examples of other flexible sheet materials containing adhesively secured water-swellable clays are found in the following <patcit id="pcit0003" dnum="US4467015A"><text>U.S. Pat. Nos. Clem 4,467,015</text></patcit>; <patcit id="pcit0004" dnum="US4693923A"><text>McGroarty, et al. 4,693,923</text></patcit>; <patcit id="pcit0005" dnum="US4656062A"><text>Harriett 4,656,062</text></patcit>; and <patcit id="pcit0006" dnum="US4787780A"><text>Harriett 4,787,780</text></patcit>.

0003U.K. published Patent Application <patcit id="pcit0007" dnum="GB2202185A"><text>GB 2,202,185A</text></patcit> discloses a layer of water-swellable bentonite between flexible fabric layers that have been needle punched together in a needle loom that secures the upper and lower layers together, wherein at least one of the fabric layers is a non-woven textile material.

0004Another waterproofing barrier, disclosed in <patcit id="pcit0008" dnum="US4344722A"><text>Blais U.S. Pat. No. 4,344,722</text></patcit>, is constructed in the field by applying a first flexible, water-permeable fabric layer, overlaying a thickness of water-swellable clay material and applying an overlay of the same flexlble, water-permeable fabric thereover. Other patents disclosing the use of water barrier layers for protecting a soil surface include British Patent Specification <patcit id="pcit0009" dnum="GB1059363A"><text>1,059, 363</text></patcit>; British Patent Specification <patcit id="pcit0010" dnum="GB1029513A"><text>1,029,513</text></patcit> and British Patent Specification <patcit id="pcit0011" dnum="GB1129840A"><text>1,129,840</text></patcit>.

0005German Patent <patcit id="pcit0012" dnum="DE3704503C2"><text>DE 37 04 503 C2</text></patcit> discloses an article having two fabric layers including one non-woven fabric, surrounding a bentonite clay layer wherein the two fabric layers are needle punched together. <patcit id="pcit0013" dnum="US4565468A"><text>Crawford U.S. Pat. No. 4,565,468</text></patcit> discloses an article including two fabric layers surrounding a bentonite clay layer wherein the two fabric layers are quilted together in a pattern forming four sided compartments.

0006While the articles described in the above-mentioned patents are effective for waterproofing against the penetration of relatively non-contaminated water, they are unable to prevent the penetration of salt (e.g., NaCl) containing water, such as ocean water. This assignee's <patcit id="pcit0014" dnum="US5389166A"><text>U.S. Patent No. 5,389,166</text></patcit>, hereby incorporated by reference, describes incorporating a water swellable clay into a mat while laying down fiber to form the mat.

0007Surprisingly it has been found that a partially cross-linked copolymer of acrylamide/partially neutralized polyacrylic acid, preferably acrylamide/potassium acrylate or sodium acrylate/acrylic acid copolymer (CAS# 312-12-13-2), e.g., STOCKOSORB, or STOCKOSORB S, from Stockhausen, Inc. of Greensboro, NC, will waterproof surfaces against the penetration of high conductivity water. The articles described herein are most useful to provide a water barrier against multivalent ion-containing water having a conductivity of at least 1 mS/cm, preferably at least 10 mS/cm, more preferably at least 30 mS/cm, even more preferably at least 40 mS/cm, and most preferably at least 50 mS/cm.

0008Super absorbent polymers ("SAPs") have been produced since the 1970s for use in a variety of products including, amongst others, hygiene products, such as disposable diapers, training pants, feminine hygiene products and incontinence devices, agricultural and horticultural products and industrial and environmental absorbents. SAPs are primarily utilized to increase or enhance the product's water-absorbency.

0009SAPs are produced from a variety of components by a variety of processes. For example, SAPs are often made from monomers such as acrylamide, acrylic acid and acrylate, which are particularly suitable for application in hygiene products.

0010Alternately, swelling clays, such as sodium smectite clays, e.g., sodium bentonite may be used to provide water-absorbency to a product. With respect to cost, the cost of swelling clays tends to be minimal compared to that of the chemical monomers described above. In addition, swelling clays are relatively stable compared to chemical monomers and are not as subject to degradation. However, swelling clays have a water absorption capacity significantly less than that of SAP, and like the common partially cross-linked partially neutralized acrylic acid copolymer SAPs, sodium smectites do not have sufficient free-swell when contacted by high conductivity salt water to act as a salt water barrier.

0011Some products include both an SAP and a swelling clay, as described in <patcit id="pcit0015" dnum="US6610780B"><text>U.S. Patent No. 6,610,780</text></patcit> and this assignee's <patcit id="pcit0016" dnum="US6783802B"><text>U.S. Patent No. 6,783,802</text></patcit>, hereby incorporated by reference. Neither the SAPs nor the water-swellable clays, however, have been capable of waterproofing surfaces against the penetration of high conductivity ion-contaminated water, such as ocean water.

0012It is well known that the montmorillonite group of clays hydrate and swell in fresh water but the swelling is substantially inhibited in salt contaminated water. Salt contaminated water is often encountered in the environments of use of bentonite clays where bentonite is advantageously employed for its swelling capacity, for example, as an additive in drilling muds for the purpose of sealing fissures in earthen formations surrounding the drill hole to prevent loss of drilling fluid; and in the sealing of lagoons and landfills. When contacted with salt contaminated water, the swelling capacity and stability of common montmorillonite clays are severely inhibited making it necessary to use much greater quantities of the clay to achieve the degree of swelling needed for sealing purposes. In some cases the palygorskite clays are used instead of the montmorillonite clays because of their better dispersing properties in salt water, as disclosed in <patcit id="pcit0017" dnum="US4202413A"><text>U.S. Patent No. 4,202,413</text></patcit>.

0013In the past, modified bentonite clays have been developed by this assignee having a swelling capacity substantially less inhibited in salt water. Examples of such modified bentonites are the polymer treated bentonites disclosed in the Clem <patcit id="pcit0018" dnum="US3949560A"><text>U.S. Patent Nos. 3,949,560</text></patcit>; <patcit id="pcit0019" dnum="US4021402A"><text>4,021,402</text></patcit>; <patcit id="pcit0020" dnum="US4048373A"><text>4,048,373</text></patcit> and <patcit id="pcit0021" dnum="US4103499A"><text>4,103,499</text></patcit>.

0014The assignee's <patcit id="pcit0022" dnum="US4634538A"><text>U.S. 4,634,538</text></patcit> teaches that one or more gums, such as xanthan gum, can be added to a water-swellable clay to improve its free swell when hydrated with salt-contaminated water. This assignee's <patcit id="pcit0023" dnum="US5578219A"><text>U.S. Patent No. 5,578,219</text></patcit> describes impregnating a dried, water-swellable clay with an aqueous solution of a water-soluble polymer followed by re-drying to improve the ability of the clay to absorb contaminated water.

0015Partially cross-linked acrylamide/sodium or potassium acrylate/acrylic acid copolymers have been used for retention of water and plant nutrients in agriculture by mixing the copolymers in soil for contact with, and as a water and nutrient source for, plants roots, but have not been recognized to provide sufficient free swell when in contact with salt-contaminated (high conductivity) water for purposes of waterproofing salt-contaminated water-contacting surfaces, as described in <patcit id="pcit0024" dnum="US20070044528A"><text>U.S. Patent Publication No. 2007-0044528</text></patcit>-awl and <patcit id="pcit0025" dnum="US5317834A"><text>U.S. Patent No. 5,317,834</text></patcit>.

SUMMARY

0016The articles and methods described herein are based on the discovery that agricultural grade superabsorbent polymers partially cross-linked (water insoluble) copolymers of acrylamide/partially neutralized acrylic acid, particularly potassium and/or sodium acrylate, have exceptional and unexpected free swell when in contact with high conductivity water or multivalent ion-containing-contaminated water The articles of manufacture described herein all include a partially cross-linked acrylamide/acrylate/acrylic acid copolymer and are used for waterproofing against high conductivity salt-containing water. More particularly, the partially cross-linked acrylamide/acrylate/acrylic acid copolymers, described herein, in accordance with a preferred embodiment of the present invention, are incorporated into sheet or roll form as waterproofing geotextile articles; or are incorporated into reformable, putty-like consistency articles for waterproofing concrete joints and the like <i>(see</i><patcit id="pcit0026" dnum="US4534926A"><text>U.S. Patent No. 4,534,926</text></patcit>, hereby incorporated by reference) by substituting the agricultural grade SAPs described herein for the bentonite clay of the <patcit id="pcit0027" dnum="US4534926A"><text>4,534,926</text></patcit> patent. The sheet or roll form geotextile articles of manufacture described herein are self-healing (will seal cuts, cracks and fissures caused in adjacent water barrier sheets or films during or after installation) and are particularly effective in sealing seems between two water barrier substrates, e.g., concrete sections and between adjacent, geocomposite liners in contact with high conductivity salt water.

0017In the geocomposite articles of the invention the partially cross-linked acrylamide/acrylate/acrylic acid copolymers are included as a safety layer under a separate, water barrier sheet material or membrane layer.

0018Accordingly, one aspect of the articles and method described herein is to provide an acrylamide/acrylate/acrylic acid copolymer that has sufficient free swell when in contact with high conductivity water such that the copolymer can provide a barrier to seal against penetration of the contaminated water.

0019Another aspect of the articles and methods described herein is to provide multi-layer geocomposite articles including a polymeric barrier layer, a woven or non-woven layer, and an intermediate layer of a partially cross-linked acrylamide/acrylate/acrylic acid copolymer that has sufficient free-swell when contacted by high conductivity water such that if a crack or rupture occurs in the polymeric barrier layer, the confined copolymer will swell sufficiently upon salt water contact to fill the crack or rupture to heal the crack or rupture and prevent further salt water leakage.

0020The above and other aspects and advantages will become apparent from the following detailed description taken in conjunction with the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

0021<figref idref="f0001">FIG. 1</figref> is a graph showing the free swell volume (2 grams of material in an excess of the aqueous salt solution) of the partially cross-linked acrylamide/acrylate/acrylic acid copolymers in aqueous 1.0% NaCl and 4.5% sea salt compared to a standard, partially cross-linked acrylate/acrylic acid copolymer SAP (Favor SXM 880) and a water swellable sodium bentonite (SPV) clay;

0022<figref idref="f0002">FIGS. 2</figref> and <figref idref="f0003">3</figref> are schematic views of apparatus and methods of manufacture used to make the geocomposite articles useful as salt water barriers in accordance with the present invention;

0023<figref idref="f0002">FIGS. 2A, 2B, and 2C</figref> are enlarged partially broken-away side views of various waterproofing geocomposite articles made in accordance with different embodiments of the present invention;

0024<figref idref="f0004">FIG. 4</figref> is a perspective view of a geocomposite article described herein oriented vertically, adjacent to a sea/soil interface.

0025<figref idref="f0005">FIGS. 5A and 5B</figref> are schematic views of test geocomposite articles with and without 1 inch slits that were tested under four meters of head salt water pressure comparing salt water barrier properties of articles with and without the partially cross-linked acrylamide/acrylate/acrylic acid copolymer, resulting in the data shown in the graphs of <figref idref="f0006">FIGS. 6</figref> and <figref idref="f0007">7</figref>; and

0026<figref idref="f0006">FIGS. 6</figref> and <figref idref="f0007">7</figref> are graphs showing that test geocomposite articles, as described herein, containing a 1 inch slit therethrough, will provide copolymer healing of the slit by the confined copolymer swelling under a 4 meter head of high conductivity salt water.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

0027The present invention may be understood more readily by reference to the following detailed description of the invention and the examples provided therein. It is to be understood that this invention is not limited to the specific components, articles, processes and/or conditions described, as these may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

0028Ranges may be expressed herein as from "about" or "approximately" one particular value and/or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment.

0029Conductivity is a measure of the level of ion concentration of a solution. The more salts, acids or bases are dissociated, the greater the conductivity of the solution. In water or wastewater it is mainly a matter of the ions of dissolved salts, and consequently the conductivity is an index of the salt load in wastewater. The measurement of conductivity is generally expressed in S/cm (or mS/cm) which is the product of the conductance of the test solution and the geometric factor of the measuring cell. For purposes of this invention, high conductivity waters are defined as waters with conductivity greater than 1 mS/cm. Conductivity can be measured using a variety of commercially available test instruments such as the Waterproof PC 300 hand-held meter made by Eutech Instruments/Oakton Instruments.

0030In the preferred embodiment, the partially cross-linked acrylamide/acrylate/acrylic acid copolymer is incorporated as a layer between a water barrier sheet or film barrier layer, preferably a polymer sheet material or membrane layer, and a woven or non-woven geotextile sheet material fabric layer. The polymer sheet material layer would be disposed in contact with the high conductivity water and the copolymer is disposed adjacent to the polymer sheet material layer between the membrane and the fabric layers to perform the function of a safety layer to prevent the flow of high conductivity water through the article if the polymer sheet material layer is defective or develops a crack or hole during installation or during use. Alternatively, the copolymer can be incorporated into the intersticies of the geotextile fabric layer to create a fabric/copolymer composite layer that serves as the safety layer attached to the membrane layer to prevent the flow of high conductivity water through the article if the polymer sheet material layer is defective or develops a crack or hole during installation or during use.

0031The partially cross-linked acrylamide partially neutralized acrylic acid copolymers, e.g., STOCKOSORBT^M and/or STOCKOSORB S™, have been found to have substantial free swell when contacted by high conductivity solutions. Examples of tested high conductivity aqueous solutions are 1% NaCl (conductivity of 18 mS/cm) and synthetic seawater (4.5% sea salt; conductivity of 53.2 mS/cm). The partially cross-linked acrylamide/partially neutralized acrylic acid copolymers provide substantial free swells when in contact with aqueous solutions contaminated with any, or a combination of, Na⁺, Ca⁺⁺, Mg⁺, Al⁺⁺⁺ and other multivalent cations in combination with anions that are common in sea water and other wastewaters. To achieve the full advantage of the geocomposite articles and methods described herein, the partially cross-linked acrylamide/acrylate/acrylic acid copolymers used in the geocomposite articles should have a free swell in 4.5% salt water of at least 35 ml per 2 grams of copolymer, preferably at least about 40 ml/2 grams, more preferably at least about 50 ml/2 grams. Free swells are determined by sprinkling 2 grams of powdered copolymer into a 100 ml graduated cylinder and filling the cylinder to 100 ml with 4.5% salt water. The volume of copolymer that settles to the bottom of the graduated cylinder is then measured and is the free swell.

0032In the preferred embodiment, described herein are multi-layer articles of manufacture that are salt water barrier geocomposite mats, and their method of manufacture. In the preferred embodiment, the geocomposite mat includes a pre-formed woven or non-woven geotextile fabric material, having a thickness of about 0.5 mm to about 200 mm, preferably about I mm to about 100 mm, having a layer of powdered or granular partially cross-linked acrylamide/partially neutralized acrylic acid copolymer, either in at least an upper portion of its thickness across its entire major surface, or provided in a separate layer on the geotextile sheet or fabric material. In the preferred embodiment, the powdered or granular copolymer is at least partially disposed within the pores of the geotextile fabric or mat material to surround the upper fibers, e.g., by vacuum suction, by vibrating during deposition of the copolymer thereon to allow the powdered or granular copolymer to flow by gravity and vibrational forces into the pores of the geotextile sheet or mat, or simply by virtue of being sized to be received within the pores of the contacting surface of the woven or non-woven (preferably non-woven) geotextile fabric or mat.

0033In the preferred embodiment, a liquid-impermeable cover sheet (membrane layer) is adhered to the upper major surface of the copolymer-containing geotextile fabric or mat to prevent the powdered or granular copolymer from escaping from the geotextile sheet or mat during transportation and installation, and to provide a primary water-impermeable layer to the article. Optionally, the edges of the copolymer-containing geotextile sheet or mat can be sealed, such as by providing the upper water-impermeable cover sheet slightly larger than the dimensions of the geotextile sheet or mat and gluing or otherwise adhering the extra cover sheet material to the edges of the copolymer-containing geotextile, such as by heat sealing them together. Other edge sealing options include sewing, needlepunching, and ultrasonic welding of the cover sheet to the edge of the geotextile sheet or mat, or by applying a separate, edge-covering material that can be glued, heat sealed or ultrasonically welded to the water-impenneable cover sheet and/or to the geotextile sheet or mat. Edge sealing materials preferably are liquid-impermeable.

0034In addition to the layer of partially cross-linked acrylamide/ partially neutralized acrylic acid copolymer, powdered or granular materials can be admixed with the copolymer or can be applied as a separate layer. The additional powdered or granular materials include water-swellable sodium smectite clay, organophilic clay, activated carbon, coke breeze, zero-valent iron, apatite, zeolite, peat moss, polymeric ion exchange resins, polymeric adsorbents and mixtures thereof. Preferably, the copolymer is disposed adjacent to the water-impermeable sheet or film barrier layer, and also may contain other materials, admixed therewith in an amount up to about 80% by weight of the mixture.

0035The method of manufacture permits the manufacture of a geocomposite article that includes the partially cross-linked acrylamide/acrylate /acrylic acid copolymer that is structurally secure, without substantial lateral movement, and contains the swelling material either as a discrete layer between the impermeable sheet and the geotextile, uniformly distributed throughout the geotextile, or distributed as a gradient throughout the geocomposite article. The multi-layer geocomposite article can be manufactured to provide either a flexible or a rigid geocomposite article, and permits the manufacture of various modified geocomposite articles that include the salt water barrier swelling copolymer in addition to a zeolite or an organophilic clay with or without a sodium smectite water-absorbent material; the application of layer(s) of liquid-impermeable films or sheets of material over not only one, but over both major surfaces of the geocomposite article to Confine the granular or powdered copolymer material in place within the geotextile sheet or mat; the application of solid or liquid adhesive materials or compositions to glue a major unclersurface of the barrier layer to the copolymer or to the geotextile sheet material containing the copolymer for complete retention. The materials can be bonded together either mechanically (sewing, needlepunching or gluing), chemically, or physically (i.e., melting, or the like). The structure can be strengthened or reinforced by inserting one or more rigidifying materials into, or onto, the geocomposite article during manufacture, such as a sheet of perforated fiberglass; rope; cardboard; relatively rigid, liquid-penneable corrugated materials, e.g., corrugated cardboard, and the like at some point at or between the top and bottom major surfaces of the geocomposite article to provide various degrees of flexibility or rigidity; the capability of manufacturing the geocomposite articles without the necessity of a consolidation step; and providing various sizes, shapes and weights of geotextiles to achieve the benefits of each.

0036The copolymers described herein are lightly cross-linked, i.e., have a crosslinking density of less than about 20%, preferably less than about 10%, and most preferably about 0.01% to about 7%. The crosslinking agent most preferably is used in an amount of less than about 7 wt%, and typically about 0.1 wt%, based on the total weight of monomers. Examples of crosslinking polyvinyl monomers include, but are not limited to, di, tri or other multifunctional acrylic, methacrylic, vinyl ether or acrylamido functional compounds that are well known in the art.

0037The relative amounts of the acrylamide; acrylate; and acrylic acid in the salt water-waterproofing copolymers described herein can vary widely from about 1 mole percent to about 99 mole percent of each in the copolymer. Best results for achieving excellent free swells in high conductivity water are achieved where acrylamide forms about 5% to about 90 mole % of the copolymer, preferably about 15% to about 60 mole %; sodium and/or potassium acrylate forms about 2% to about 50% mole % of the copolymer, preferably about 5% to about 25 mole % of the copolymer; and acrylic acid forms about 2% to about 50% of the copolymer, preferably about 1% to about 10% mole of the copolymer. Other material compositions that give a free swell of greater than about 35 mL/ 2 grams material in 4.5% sea salt in water are envisioned for this invention. Other monomers can be present in the copolymer including acrylic and methacrylic esters and acids, and substituted acrylamide and methacrylamides provided that the other monomers do not retract from the ability of the copolymer to absorb high conductivity water.

0038As shown in <figref idref="f0002">FIGS. 2</figref> and <figref idref="f0003">3</figref>, there is illustrated a method and apparatus, including a number of optional features each of which can be used alone or in combination with any of the other features for manufacturing a product having only a partially cross-linked acrylamide/acrylate/acrylic acid powdered or granular material therein, or a plurality of different granular or powdered materials, including the copolymer, and with or without various reinforcing materials and/or coating materials added to one or both exterior surfaces of the article being manufactured to provide various characteristics or properties to the finished salt water geocomposite barrier articles 10, as will be described in more detail hereinafter. The apparatus generally includes a conveyor belt 17 that travels continuously around a pair of rollers 18 and 20, at least one of which is motor driven at a desired speed; and one or more powdered or granular material feeding devices, generally designated by reference numerals 22 and 24.

0039A liquid-impermeable sheet material layer 14, used to provide a primary salt water barrier sheet is applied to an upper major surface of a pre-formed, geotextile sheet or mat 15 after loading the geotextile sheet or mat 15 with the a partially cross-linked acrylamide/acrylate/acrylic acid copolymer 16 from one or both feeding devices 22 and/or 24. In one embodiment, the powdered or granular copolymer 16 penetrates the geotextile sheet or mat 15 by vibrating the geotextile 15 with vibrator 140. Alternatively, vacuum can be applied under the geotextile sheet or mat 15. Alternatively, the copolymer 16 minimally penetrates into an upper surface of the geotextile sheet or mat 15 to form a distinct copolymer layer disposed between the geotextile sheet or mat 15 and the primary waterproofing barrier layer 14.

0040Additional granular or powdered materials can be applied to the geotextile sheet or mat 15 from feeding conduits 22 or 24 to provide one or more surface concentrations of copolymer 16 or to apply a different powdered or granular material, prior to applying the water-impenneable cover layers 14. The primary barrier layer 14 preferably is adhered to the upper major surface of the copolymer-containing geotextile sheet or mat 15 using a water-insoluble adhesive, applied from adhesive supply vessel 34. Other nonlimiting methods of introduction of the copolymer into the composite structure can be envisioned. Alternative methods could include: the coating or spraying of a paste or dispersion of the copolymer onto the sheet via extrusion or roll coating; preassembling a copolymer/fabric composite to be later combined with a water-impenneahte layer to form the final composite; or other methods to achieve the desired structure.

0041<figref idref="f0002">FIG. 2A</figref> shows at geotextile sheet or mat 15 filled only on an upper major surface with the powdered or granular copolymer material 16. <figref idref="f0002">FIG. 2B</figref> shows the geotextile sheet or mat 15 filled with the copolymer 16 incorporated throughout the geotextile sheet or mat 15. <figref idref="f0002">FIG. 2C</figref> shows the partially embedding of the copolymer 16 into an upper surface of the geotextile (preferably non-woven) sheet or mat 15, a distinct intermediate layer of copolymer, and an adhesively secured upper, primary, water-impermeable sheet material layer 14. Other layers of material could be envisioned to assist in improvement of the mechanical strength of the composite, to assist with the containment of the copolymer in the structure, or improve the bonding of the different layers of the structure.

0042Turning now to <figref idref="f0003">FIG. 3</figref>, there is shown a schematic diagram of one method of loading the pre-formed, high loft geotextile mat 115 with powdered or granular copolymer in a dry state. The dry material feeding apparatus, generally designated by reference numeral 100 is useful for depositing the partially cross-linked acrylamide/acrylate/acrylic acid copolymer, with or without other powdered or granular materials, such as an organophillic clay or other materials, from a receiving hopper 102. An auger 104 is disposed at a lower end of the receiving hopper 102, and in fluid communication therewith, to force the copolymer material through conduit 106 to an inlet 108 of elevator 110. The copolymer is discharged from the elevator 110 at elevator outlet opening 112, through conduit 114 into a receiving hopper 116. A pair of augers 118 and 120 in fluid communication with a lower portion of hopper 116 force the copolymer into one, two or three feeding mechanisms, generally designated by reference numerals 122, 124 and 126, for feeding the copolymer in a controlled manner to one, two or three continuous feed conveyor belts 128, 130 and 132 successively aligned above an elongated product conveyor belt 134.

0043The copolymer generally is applied over the geotextile sheet or mat 115 in an amount of about 0.1 ounce to 3 pounds of powdered or granular copolymer per square foot of finished article major surface area, preferably about 0.1 ounce to about 5 pounds of powdered or granular copolymer per square foot of article major surface area. In accordance with one embodiment, a supply of a liquid-impermeable flexible sheet material 136 in roll form 138 may be disposed above the continuous product conveyor belt 134 to provide a continuous supply of liquid-impermeable flexible sheet material onto an upper surface of the product conveyor belt 134. The upper surface of sheet material 136 from roll 138 may be sprayed with liquid adhesive from adhesive vessel 139 to adhere the sheet material to an undersurface of the geotextile sheet or mat 115, and the powdered or granular copolymer then is deposited onto the geotextile sheet or mat 1 15 from one, two or all three of the feed conveyor belts 128, 130 and 132. Any one, two or all three of the feed conveyor belts 228, 230 and 232 can be used to incor-porate the same or different powdered or granular materials throughout a portion of, or the entire thickness of the geotextile sheet or mat 115. Vibration apparatus 140 may be connected to the product conveyor belt directly below the feed conveyor belts 128, 130, and 132 to vibrate the powdered or granular contaminant-reactant materials into the geotextile sheet or mat 115.

0044The powdered or granular copolymer is deposited across the entire width of the geotextile sheet or mat 115, as the particles drop from the feeders 122, 124 and/or 126. In this manner, the entire thickness or any portion of the thickness of the fibrous mat 115 may be filled with the copolymer. Dust collection suction devices 144, 146 and 148 may be disposed near each continuous feed conveyor belt 128, 130 and 132 to clear the air of fine particles emanating from feeding mechanisms 122, 124 and 126 and return the particles back to a dust collector 167 for disposal and/or back to the receiving hopper 102, via conduit 149. A second flexible, water-impermeable sheet material 150, from roll 151, is disposed on a downstream side of the copolymer feeding mechanisms 122, 124, and 126 and above the product conveyor belt 134. The second flexible sheet material 150 is fed by power driven roller 152, power rollers 154 and 156 and wind up rollers 158 and 160 to dispose a flexible, water-impermeable sheet material 150 on top of the contaminant-reactant-containing article to dispose the geotextile sheet or mat 115 and the separate, or geotextile-contained copolymer, between lower flexible sheet material 136 between the geotextile sheet or mat 115 and the upper flexible, water-impermeable primary barrier layer 150. Adhesive vessel 161 preferably applies adhesive to a surface of sheet material 150 to adhere the sheet material 150 to an upper surface of the copolymer-containing geotextile sheet or mat 115.

0045The copolymer functions to absorb high conductivity multivalent ion-containing salt water regardless of its particle size. The powdered or granular copolymer preferably has a particle size in the range of about 10µm to about 500µm, preferably about 50µm to about 1,000µm, more preferably about 50µm to about 800 um, and most preferably a particle size distribution of about 50µm to about 800µm containing up to 100% of the particles in the 50µm to 200µm range, preferably about 10wt% to about 50wt% in the 50µm to 200µm range, with 50 to 90wt.% of the particles in the 200µm to 800µm size range..

0046As shown in <figref idref="f0005">FIG. 5</figref>, the geocomposite articles 10 containing the partially cross-linked acrylamide/acrylate/acrylic acid copolymers described herein are particularly effective for vertical disposition adjacent to a sea/soil interface 200 for protecting the soil interface from salt water penetration by ocean 202 which would otherwise penetrate the sea/soil interface 200 into soil 204.

0047The geotextile sheet or mat 15 or 115 can be woven or non-woven, preferably non-woven. Suitable fibers of construction of the geotextile mat 15 or 115 include fibers made from rayon, polypropylene, polyesters, nylon, acrylic polymers and copolymers, ceramic fiber, fiberglass, propylene-ethylene copolymers, polypropylene-polyamide copolymers, a single monofilament, polyethylene, polyurethane, cotton, jute and any other non-biodegradable, or very slowly biodegradable, fibers preferably having both bacteriological, hydrolytic and chemical resistance. In some installations, the thickness of the article is not important and such articles can be formed with any desired thickness, e.g., 3 mils to about 4 inches containing about 0.1 oz to about 30 pounds per square foot of contaminant-reactant material.

0048The above-described products can be modified in a number of ways to suit various purposes and this adaptability of the products is one of the primary benefits when compared with water barriers of the prior art. For example, the geocomposite products described herein can be loaded with a heavy material such as metal screen, or a heavy mineral such as Barite, iron oxide or the like, relatively uniformly, together with the powdered or granular copolymer so that the overall product has a specific gravity greater than 1.0 thereby enabling the material to submerge easily in water. Accordingly, the product can be applied to the soil surface at the bottom of a filled lagoon, waste containment area, and the like, without first draining the lagoon or waste containment area. The product containing a heavy mineral can be rolled out over the water or waste containment upper level and allowed to sink to cover the soil surface at the bottom of the water or liquid waste material, thereby saving substantial time, effort and expense in sealing a pre-existing lagoon, waste containment area, and the like, without first draining the lagoon or waste containment area.

0049In another embodiment, the products described herein can have incorporated therein a very light material such as expanded vermiculite or expanded perlite, so that the product has substantial buoyancy in water, liquid waste materials, and the like, to form a cover over a liquid waste containment area, such as a toxic waste lagoon, to prevent external compounds, dust, and dirt from entering the waste containment area. One portion of this cover material can be adapted for removal or rolling back so that additional toxic waste and the like may be added to the covered containment area while maintaining a water-impervious cover to prevent further filling of the waste containment area with rain water.

0050The products described herein can be essentially a single copolymer-containing, non-woven fabric material, adhered to a water-impermeable cover layer, e.g., polyvinyl chloride (PVC) primary barrier sheet. Preferably, the geocomposite article includes an upper barrier layer, such as a polyvinyl chloride (PVC) sheet material adhesively secured to a woven or non-woven sheet material containing the partially cross-linked acrylamide/acrylate/acrylic acid copolymer. Further, drainage structures and other articles used in the water drainage arts can be virtually incorporated into the interior of this product during manufacture, e.g., under the upper cover sheet. Herbicides, bactericidal materials, tracer chemicals, various colorants that indicate contact with a particular chemical or class of chemicals, and the like, also can be incorporated into the articles described herein.

0051The product is particularly effective in shored wall conditions for application against steel sheet piling; soldier beam and lagging; soldier beam and earth installations; concrete caissons; earthen stabilized wall structures and diaphragm wall structures.

0052The uses for the powdered or granular material-filled or partially-filled products described herein are virtually infinite since the product can be made completely flexible, relatively rigid or rigid and can be applied against very contoured and slopping surfaces, rough or smooth, as well as vertical surfaces, such as foundation walls, dams, along the sides of canals and below grades such as in tank farms, and for irrigation and water conservation techniques.

0053In order to demonstrate the "healing" capacity of the partially cross-linked acrylamide/acrylate/acrylic acid copolymers described herein, geocomposite test articles were prepared from a PVC sheet material geomembrane having a thickness of .045 inch adhesively secured (using 2.30 grams of Bostik Supertak Aerosol Adhesive) to a non-woven polyethylene terephthalate (PET) fabric material containing 2.96 grams of STOCKOSORB S (partially cross-linked acrylamide/acrylate/acrylic acid copolymer) sandwiched between the geomembrane and the fabric layers. The PVC and PET sheet materials were circular sheets each 10 cm in diameter, having a surface area of 78.54 cm². The geocomposite test articles were cut with a 1 inch slit through all layers, as shown in <figref idref="f0005">FIG. 5</figref>.

Test Procedure: Self-Flealing Performance

0054The geocomposite test articles were cut into 10 cm diameter circles. The test samples were then were cut with a 1-inch slit through all layers, as shown in <figref idref="f0005">Figure 5</figref>, to simulate damage to the geomembrane. The slit samples were then placed in a circular test cell, sealed at its edges, at the bottom of a water tower to provide 4 meters of salt water (4.5 wt. % Sea Salt; 53.2 mS/cm Conductivity) head pressure. A porous stone and weight were placed on top of the slit to simulate a confining pressure on the sample of 20lbs/ft² without preventing the access of the sea salt solution to the slit. The test cell is then filled with the test solution exposing the test sample to the saltwater under the specified conditions. The amount of salt water that flows through the slit in the test sample is collected and measured at regular time intervals. Testing is conducted for as long as is practical for samples that exhibit poor self healing and for a minimum of 24 hours for samples that exhibit good self healing. Typical results of the testing are shown in <figref idref="f0006">FIG. 6</figref>.

Data Analysis

0055The fluid flow vs. time is plotted for the geocomposite test article sample and the data is evaluated to determine the slope of the curve (flow rate in mL/min) once the fluid flow has reached steady state. The fluid flow of a geocomposite control sample is also measured. The geocomposite control sample consists of the water-impermeable membrane employed with the test sample without an active self healing layer. The test apparatus is evaluated after the test to make sure that test cell failure did not compromise results.

0056The performance of the test sample is reported as the "self-healing performance index" or "SPI" which is calculated according to the following formula: SPI = S_T/S_C, wherein S_T = Flow rate of fluid through the slit in the sample (mL/min) after steady state flow has been achieved, wherein S_C = the Flow rate through a control sample (mL/min) after steady state flow has been achieved.

0057To achieve the full advantage of the articles and methods described herein, the articles tested as described above should have an SPI less than 0.1, preferably less than .01, more preferably less than 0.015, even more preferably less than 0.005 and most preferably less than 0.001. <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="16"><colspec colnum="1" colname="col1" colwidth="30mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="20mm" /><colspec colnum="10" colname="col10" colwidth="12mm" /><colspec colnum="11" colname="col11" colwidth="12mm" /><colspec colnum="12" colname="col12" colwidth="12mm" /><colspec colnum="13" colname="col13" colwidth="12mm" /><colspec colnum="14" colname="col14" colwidth="12mm" /><colspec colnum="15" colname="col15" colwidth="21mm" /><colspec colnum="16" colname="col16" colwidth="12mm" /><thead><row valign="middle"><entry align="center">Test Sample #</entry><entry align="center" /><entry align="center" /><entry align="center">15</entry><entry align="center">16</entry><entry align="center">19</entry><entry align="center">20</entry><entry align="center">21</entry><entry align="center">25</entry><entry align="center">26</entry><entry align="center">28</entry><entry align="center">29</entry><entry align="center">30</entry><entry align="center">31</entry><entry align="center">32</entry><entry align="center">33</entry></row></thead><tbody><row><entry align="center">Core</entry><entry align="center">Control*</entry><entry align="center">Control 2**</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry><entry align="center">PVC</entry></row><row><entry align="center">Ag SAP g/sq ft</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">35</entry><entry align="center">35</entry><entry align="center">35</entry><entry align="center">35</entry><entry align="center">35</entry><entry align="center">35</entry><entry align="center">35</entry><entry align="center">42</entry><entry align="center">42</entry><entry align="center">28</entry><entry align="center">28</entry><entry align="center">28</entry><entry align="center">35</entry></row><row><entry align="center">Standard SAP</entry><entry align="center">0</entry><entry align="center">35</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry></row><row><entry align="center">Time to Seal (min)</entry><entry align="center">N/A</entry><entry align="center">N/A</entry><entry align="center">60</entry><entry align="center">330</entry><entry align="center">40</entry><entry align="center">14</entry><entry align="center">0</entry><entry align="center">355</entry><entry align="center">30</entry><entry align="center">2</entry><entry align="center">60</entry><entry align="center">70</entry><entry align="center">1</entry><entry align="center">16</entry><entry align="center">1</entry></row><row><entry align="center">Volume to Seal (mL)</entry><entry align="center">N/A</entry><entry align="center">N/A</entry><entry align="center">401</entry><entry align="center">206</entry><entry align="center">119</entry><entry align="center">198</entry><entry align="center">0</entry><entry align="center">372</entry><entry align="center">60</entry><entry align="center">4</entry><entry align="center">202</entry><entry align="center">241</entry><entry align="center">0</entry><entry align="center">164</entry><entry align="center">0.8</entry></row><row><entry align="center">Water Conductivity</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry><entry align="center">53.2</entry></row><row><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry align="center">SS Flow Rate mL/min</entry><entry align="center">139.4</entry><entry align="center">2.32</entry><entry align="center">0</entry><entry align="center">0.0577</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0.00750</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0.011</entry><entry align="center">0</entry></row><row><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry align="center">SPI</entry><entry align="center">N/A</entry><entry align="center">0.01665</entry><entry align="center">0</entry><entry align="center">4.135x10^-4</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">5.379-10^-5</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">0</entry><entry align="center">7.889x10^-5</entry><entry align="center">0</entry></row></tbody></tgroup><tgroup cols="16" rowsep="0"><colspec colnum="1" colname="col1" colwidth="30mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="12mm" /><colspec colnum="8" colname="col8" colwidth="12mm" /><colspec colnum="9" colname="col9" colwidth="20mm" /><colspec colnum="10" colname="col10" colwidth="12mm" /><colspec colnum="11" colname="col11" colwidth="12mm" /><colspec colnum="12" colname="col12" colwidth="12mm" /><colspec colnum="13" colname="col13" colwidth="12mm" /><colspec colnum="14" colname="col14" colwidth="12mm" /><colspec colnum="15" colname="col15" colwidth="21mm" /><colspec colnum="16" colname="col16" colwidth="12mm" /><tbody><row><entry namest="col1" nameend="col16" align="justify">*Control: no partially cross-linked acrylamide/acrylate/acrylic acid copolymer (Ag. Grade SAP) **Control 2: Partially cross-linked acrylate/acrylic acid copolymer (conventional SAP) only</entry></row></tbody></tgroup></table></tables>

0058As seen in <figref idref="f0006">FIG. 6</figref>, a control test geocomposite article, containing the PVC layer adhesively secured to the non-woven PET layer, with no copolymer carried by the non-woven, had rapid, linear salt-water leakage of about 139.4 ml/min. The geocomposite articles constructed as described herein, containing the partially cross-linked acrylamide/acrylate/acrylic acid copolymer (Run #1 through Run #7 - <figref idref="f0006">FIG. 6</figref>) that exhibited salt water leakage in the first 20-30 minutes until the copolymer was sufficiently swelled by the salt water and sealed off the PVC slit. After about 30 minutes, there was little to no additional salt water leakage through the slit in the geocomposite article.

0059<figref idref="f0007">FIG. 7</figref> shows the results of the control of <figref idref="f0006">FIG. 6</figref> (PVC plus non-woven without copolymer) and Run #1 through Run #7 over 1440 minutes. The control sample shows continued leakage while the Runs #1 - 7 show essentially no salt water leakage after 20-30 minutes.