WO2013141821A1

WO2013141821A1 - Boring bivalve resistant polymer composition

Info

Publication number: WO2013141821A1
Application number: PCT/TH2012/000011
Authority: WO
Inventors: Roman Strauss; Sanchai THONGKHAM
Original assignee: Irpc Public Company Limited
Priority date: 2012-03-22
Filing date: 2012-03-22
Publication date: 2013-09-26
Also published as: AU2012374106A8; AU2012374106A1; AU2012374106B8; AU2012374106B2

Abstract

The present disclosure relates generally to a composition such as a polymer composition for controlling marine borers by way of preventing, resisting, or delaying damage caused by boring bivalve larvae intrusion. In several embodiments a marine borer resistant composition includes at least one carrier material such as a set of base polymers intended for exposure to a liquid environment in which marine borers are expected to exist, and a phthalocyanine compound at a predetermined concentration relative to the set of base polymers sufficient for at least substantially reducing a likelihood of marine borer intrusion into the carrier material(s) or the set of base polymers that can prevent, resist, or delay damaged caused by boring bivalves. In particular embodiments the composition includes one of copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, and nickel phthalocyanine. Additionally, the present disclosure describes a process for producing an article intended for exposure to a liquid environment in which marine borers are expected to exist, where the article includes an anti-marine-borer composition or anti-marine-borer agent in accordance with the present disclosure.

Description

BORING BIVALVE RESISTANT POLYMER COMPOSITION

Technical Field

The present disclosure relates generally to a polymer composition for controlling marine borers. More specifically, an embodiment of the present disclosure relates to a polymer composition intended for prolonged or long duration exposure to an aquatic environment in which boring bivalves are expected to be present, where the polymer composition includes a predetermined concentration of a phthalocyanine compound therein for preventing, resisting, or delaying damage caused by boring bivalve larvae.

Background

In marine environments, perforation of piping systems or man-made structures caused by boring bivalves or other maritime organisms results in undesirable loss of structural integrity, and in several situations rapid structural destruction of such systems. Wood has been typically used in marine applications. Several techniques to prevent, control or delay biodeterioration of wood in underwater environments are known, including creosote treatment as a preservative or incorporation of chlorothalonil. However, in situations or environments where wood is not suitable, or wood biodeterioration techniques fail to adequately prevent biodeterioration, or wood preservation involving toxic and leachable chemicals is not an alternative, plastics or polymers are often used as wood substitutes or replacements.

Plastics or polymers have been increasingly used as marine construction materials for structures such as pipes, rods, sheets, containers, tanks, buoys. Plastics or polymers used in marine environments include polyolefin (such as HDPE, PP), polystyrene (PS), polyvinyl chloride (PVC), acrylonitrile butadiene styrene (ABS), and polycarbonate (PC). It has become common practice to select such plastics for the construction of submarine pipes or structure because they have been considered to be inherently immune to intrusion or penetration by boring organisms. More recently, however, it has been reported that these plastics may not necessarily be immune to intrusion by boring organisms such as boring bivalves. H.A. Jenner et al. (2003) have reported in "Perforation of ABS pipes by boring bivalve Martesia striata: a case study", International Biodeterioration & Biodegradation, 52, page 229-232, that ABS pipes may not necessarily be immune to penetration by wood boring pholads, particularly Martesia striata. Jenner et al. further indicated that Martesia striata caused heavy damage by drilling holes with a size ranging from 3 to 19 mm² in ABS pipes used for hypochlorite transportation. PVC piping system on the north coast of Java failed to resist attack by Martesia striata, and pipe failure occurred in approximately one year, as published by P.J.B. Scott, "Rapid Destruction of PVC Piping by Boring Bivalve", International Biodeterioration, 27, page 87-92. Moreover, it has been most recently found by IRPC Company Limited that High Density Polyethylene (HDPE) pipes installed underwater at Pee Lok canal in Samutsongkram province, Thailand, exhibited serious damage by boring bivalve shells as illustrated by FIG. 1 only after 1.5 years in service.

In general, there is no material known in the art that is absolutely immune to boring bivalve attack. Accordingly, there exists a need for a material that can prevent, resist, or significantly delay damage caused by bivalve boring larvae during usage of such material in submarine applications. The prevention, resistance, or delay of damage to underwater materials or structures can provide enhanced economic value due to prolonged material or structure service years or life span, as well as enhanced safety due to no or reduced leakage from materials or structures such as underwater piping systems.

Summary

In one aspect, a marine borer resistant composition includes a set of base polymers intended for exposure to or immersion in an aquatic environment in which marine borers are expected to exist and a phthalocyanine compound at a predetermined concentration relative to the set of base polymers sufficient for at least substantially reducing a likelihood of marine borer intrusion into the set of base polymers. In a further aspect, the composition includes one of copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, and nickel phthalocyanine. In another aspect, the composition according to the present disclosure can include copper phthalocyanine at the concentration of at least approximately 0.01 phr. The marine borer resistant composition according to the present disclosure can prevent intrusion of marine borers therein for at least approximately 12 months.

In the second aspect, a process for producing an article intended for exposure to or immersion in an aquatic environment in which marine borers are expected to exist includes providing a set of base polymers intended for immersion in the aquatic environment; providing a phthalocyanine compound at a predetermined concentration relative to the set of base polymers, the phthalocyanine compound sufficient to at least substantially reduce a likelihood of marine borer intrusion into the set of base polymers; combining the set of base polymers and the phthalocyanine compound; and forming an article having a surface that includes the set of base polymers and the phthalocyanine compound, the surface of the article intended for exposure to the aquatic environment. In another aspect, the article intended for exposure to the aquatic environment can be a portion of a pipe, a rod, a sheet, a liquid receptacle such as a container or a tank, a sheet or liner, a boat, a swimmer, a buoy or other flotation device, a support structure, a textile, a rope, a fiber, a filament, a window, a coating, or a membrane.

Brief Description of the Figures

A description of embodiments of the present disclosure is provided below with reference to the figures, in which:

FIG. 1 shows a flowchart of a process for preparing, producing, or manufacturing and using a composition and/or article that is resistant to one or more types of marine borers (e.g., bivalve borers such as Martesia Striata) according to an embodiment of the present disclosure.

Table 1 shows representative numbers of bore holes caused by Pholadid bivalves in test specimens of multiple test groups according to an embodiment of the present disclosure. Detailed Description

In the context of the present disclosure, the term "set" corresponds to or is defined as a nonempty finite organization of elements that mathematically exhibits a cardinality of at least 1 (i.e., a set as defined herein can correspond to a singlet or single element set, or a multiple element set), in accordance with known mathematical definitions (for instance, in a manner corresponding to that described in An Introduction to Mathematical Reasoning: Numbers, Sets, and Functions, "Chapter 11 : Properties of Finite Sets" (e.g., as indicated on p. 140), by Peter J. Eccles, Cambridge University Press (1998)). In accordance with an aspect of the present disclosure, an element of a representative set can include or be a material or chemical compound, component, or constituent; a property or characteristic of a material or chemical compound, component, or constituent; a process portion; or a value.

In the description that follows, unless explicitly stated otherwise, the recitation of particular numerical values or value ranges is taken to be a recitation of particular approximate numerical values or approximate value ranges. For instance, recitation of a value such as 0.1 phr, or a value range of 0.05 - 0.5 phr, is respectively taken to be a recitation of a value of about 0.1 phr or a value range of approximately 0.05 - 0.5 phr.

Embodiments of the present disclosure relate to a formulation or composition, which in several embodiments includes or is a polymer formulation or composition, that can prevent, inhibit, discourage, or significantly delay or retard damage caused by marine borers, and in particular, boring bivalves, when the composition is exposable / exposed to or immersable / immersed in a liquid, aquatic, or marine environment in which one or more marine borer species are known or expected to exist. Such a composition can be referred to as an anti- marine-borer composition. Several embodiments of the present disclosure further relate to marine borer (e.g., boring bivalve) resistant systems, objects, structures, or structural features that are manufactured using a composition in accordance with the present disclosure, for instance, marine borer resistant pipes, conduits, channels, chambers, vessels, casings, sleeves (e.g., protective outer or inner sleeves), shutterings, windows, support members, structural repair work, or coatings or treatments (for instance, a paint, sealant, protectant, or other type of coating or layer that can be carried by or applied to objects or materials, where such objects can be polymeric or non-polymeric (e.g., wood)).

Compositions in accordance with embodiments of the present disclosure include a set of base or carrier materials or substances that carry at least one phthalocyanine compound in an amount sufficient to resist, prevent, or counter marine borer intrusion (an "anti-marine-borer agent"). Depending upon embodiment details, a base or carrier material in accordance with the present disclosure can be polymeric (e.g., a polyethylene based and/or other type of polymer) or non-polymeric (e.g., a glass material, a ceramic material, a metal, or a petroleum or hydrocarbon based material or substance). In accordance with an embodiment, an amount of an anti-marine-borer agent carried by a base or carrier material can be, for instance, between approximately 0.01 - 0.5 phr (e.g., about 0.05 - 0.10 phr) for a polymeric base or carrier material; or approximately 0.05% - 5% (e.g., about 0.10% - 1%) by weight for a non- polymeric base or carrier material.

Particular compositions such as polymer compositions in accordance with the present disclosure can prevent, inhibit, discourage, or significantly delay the incursion, intrusion, or penetration of one or more types of marine borers such as boring bivalves therein for a period of at least 3 months, or several or many months (e.g., 6 - 9 months), or one or more years (e.g., 1 - 10 years, or 2 - 5 years). Materials, structures, or objects that carry or are made using compositions in accordance with embodiments of the present disclosure on and/or within surfaces that are exposed or exposable to a marine borer environment or which are at risk of marine borer attack can prevent, inhibit, discourage, or significantly delay marine borer incursion, intrusion, or penetration into such surfaces for corresponding time periods or the duration of a service or deployment life. Compositions in accordance with embodiments of the present disclosure and portions of materials, structures, or objects that carry or incorporate such compositions are thus marine borer attack-resistant or substantially marine borer attack- proof.

Bivalve borers include Martesia Striata. With respect to aquatic or underwater applications, for instance, marine polymer piping applications, Martesia Striata larvae settle on a substrate or surface such as an exposed pipe surface, and begin drilling into or through the pipe surface by rotating around their longitudinal axis using their hard bivalve shell edges as a drilling tool. During Martesia Striata bivalve growth, a hole drilled into a polymer substrate becomes larger, and can reach several millimeters or even centimeters in depth and/or diameter, resulting in structural damage, leakage, loss of structural integrity, and/or structural collapse in one or more portions of a piping system or structure. Because Martesia Striata penetration is not assisted by a chemical dissolution (e.g., of polymer or plastic substrates), Martesia Striata can bore into or attack a wide variety of substrates. Martesia Striata does not digest polymer or plastic substrates for feeding purposes, but rather drills for purpose of sheltering and housing.

A polymer formulation or composition in accordance with various embodiments of the present disclosure includes at least one base, reference, or target polymer or plastic substance or resin that (a) is intended for exposure to or use in liquid or aquatic environments in which marine borers such as boring bivalves are expected or known to exist; and which (b) carries, incorporates, or is combined, mixed, blended, or impregnated with an active compound that includes at least one phthalocyanine compound or pigment at a concentration sufficient to inhibit or prevent marine borer intrusion, such as boring bivalve organism intrusion, into the base polymer(s). Such an active compound can be referred to as an anti-marine-borer agent. In various embodiments, a base polymer includes a polyolefin such as polyethylene (PE), more particularly high density polyethylene (HDPE), and/or polypropylene (PP). In some embodiments, a base polymer can include one or more of PVC, ABS, PS, PC, PA, or another polymer. A phthalocyanine compound or pigment can be selected from at least one of copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, and nickel phthalocyanine. In some embodiments, a phthalocyanine pigment includes or is zinc phthalocyanine. In a representative embodiment, a phthalocyanine pigment includes or is copper phthalocyanine.

Copper phthalocyanine has a molecular structure of C₃₂Hi₆Cu ₈ , and has as its chemical name (29H,31H-phthalocyaninato (2-)-N29,N30,N31,N32)copper. Copper phthalocyanine is known by a variety of names, including blue, phthalo blue, helio blue, thalo blue, Windsor blue, phthalocyanine blue, C.I. Pigment Blue 15:2, Copper phthalocyanine blue, Copper tetrabenzoporphyrazine, Cu-Phthaloblue, PB-15, PB-36, and C.I. 74160. Other trade names and synonyms include Accosperse cyan blue GT Aqualine blue, Bahama blue BC, Bermuda blue, Blue GLA, Blue phthalocyanine alpha-form, Blue toner GTNF, BT 4651, Calcotone blue GP, Ceres blue BHR, Chromatex blue BN, Chromofine blue 4920 C.I. 74160, C.I. Pigment blue 15, Congo blue B 4, Copper(II) phthalocyanine, Copper phthalocyanin, Copper beta.- phthalocyanine, Copper(2+) phthalocyanine, alpha-Copper phthalocyanine, eta-Copper phthalocyanine, Copper phthalocyanine blue, Copper tetrabenzoporphyrazine, Cromofine blue 4950, Cromophtal blue 4G, Cupric phthalocyanine, Cyan blue BNC 55-3745, Cyanine blue BB, Cyan peacock blue G, Dainichi cyanine blue B, Daltolite fast blue B, Duratint blue 1001 EM blue NCB, Euvinyl blue 702, Fastogen blue 5007, Fastolux blue, Fastolux peacock blue, Fenalac blue, B disp Franconia blue A4431, Graphtol blue, BL Helio blue B, Helio fast blue B Heliogen blue, Hostaperm blue, AFN Irgalite blue BCA, Irgalite blue LGLD, Irgalite fast brilliant blue BL, Irgaplast blue RBP, Isol fast blue B, and other names (any number of which are hereinafter referred as "copper phthalocyanine"). The chemical structure of copper phthalocyanine is shown below:

Copper phthalocyanine is previously known to be used as a blue pigment or blue color additive that can be incorporated with a polymer base resin. However, copper phthalocyanine is not previously known to be used in polymer materials, structures, or objects that are specifically intended for prolonged exposure to external liquid or aquatic environments (e.g., natural or uncontrolled marine environments, such as canals, seas, or oceans). Furthermore, copper phthalocyanine is not previously known to be used as an anti-marine-borer agent in polymer materials, structures, or objects having interior or internal surfaces that can be exposed to marine borers. Rather, copper phthalocyanine is previously known to be used as a pigment added to HDPE pipe, for providing such pipe with a blue color that facilitates ease of differentiation between or identification of the pipe and a non-aquatic external environment in which the pipe resides, such as soil (which naturally exhibits a color other than blue, such as a dark or very dark color, e.g., brown or black). The use of copper phthalocyanine to provide blue coloration to materials, structures, or objects that are intended for external exposure to an aquatic or marine environment would typically render such materials, structures, or objects less visible or distinguishable with respect to the surrounding aquatic environment, undesirably making associated identification, location, construction, maintenance, repair, or replacement procedures more difficult and/or time consuming. Additionally, the use of blue pigment such as phthalocyanine in plastic part for outdoor applications would also require additional light stabilizers for UV protection, which undesirably and significantly increases the cost.

Furthermore, copper phthalocyanine is not previously known to be an agent that can prevent, inhibit, discourage or significantly retard boring bivalve attack against polymer materials when incorporated therein. That is, copper phthalocyanine is not previously known to act as an anti-boring-bivalve agent, i.e., a boring bivalve resistive or preventative agent or counteragent. Correspondingly, the intentional or preferential incorporation of copper phthalocyanine as a boring bivalve impediment, preventative, or counteragent into materials or structures intended for significant duration, prolonged, or long term exposure to and/or at least partial immersion in liquid, aquatic, or marine environments in which boring bivalves are known or expected to exist is not previously known. The effectiveness of copper phthalocyanine as a boring bivalve counteragent when incorporated into polymer materials that are subjected to significant duration, prolonged, or long term exposure to boring bivalve environments is surprising and unexpected. Various embodiments in accordance with the present disclosure are directed to a formulation, composition, material, or structure that includes a set of base, reference, or target polymers intended for use in or exposure to aliquid or aquatic environment in which boring bivalves such as Martesia Striata are expected to be present, and which further includes at least one phthalocyanine compound such as copper phthalocyanine in an amount or concentration sufficient to act as a boring bivalve resistive agent or counteragent (e.g., a Martesia Striata resistive agent or counteragent) for preventing, at least significantly impeding or delaying, or substantially reducing the likelihood of boring bivalve intrusion, penetration, or perforation into the set of base polymers. Such a composition can be referred to as a boring bivalve resistant composition or a boring bivalve counteragent composition. Additional embodiments are directed to particular types of materials, structures, or objects that are intended for exposure to or deployment in liquid or aquatic environments or applications (e.g., underwater environments, fluid transfer / fluid communication applications, and/or object shielding or waterproofing / water-resisting applications) in which boring bivalves are known or expected to exist, and which include at least one surface (e.g, an outer or exterior surface, and/or an inner or internal surface) that (a) is exposed or exposable to such an environment; and (b) carries or incorporates a boring bivalve resistant composition in accordance with the present disclosure.

In various underwater applications or environments, a black color additive such as carbon black is added to a polymer for producing or manufacturing a black structure or object that is intended for underwater deployment. In certain instances, the carbon black also provides UV stability to the polymer or plastic materials. Embodiments of the present disclosure are directed towards the incorporation of one or more types of phthalocyanine compounds (e.g., copper phthalocyanine) at a predetermined concentration to facilitate or directly effectuate a delay, prevention, or resistance against intrusion, penetration, perforation, or attack by bivalve borers, in contrast to prior uses of phthalocyanine compound(s) intentionally or specifically for the purpose of coloration (e.g., as a colorant, coloring agent, or color additive). It is not expected or obvious to apply or incorporate a phthalocyanine compound such as copper phthalocyanine, which is generally used as a blue pigment, in underwater or submarine applications, compositions, materials, or structures in which (a) one or more other coloring agents or pigments (e.g., carbon black) can dominate, overwhelm, interfere with, or obscure the coloring performance or activity of the phthalocyanine compound as a coloring agent; or (b) the phthalocyanine compound can interfere with or obscure the coloring performance or activity of one or more other coloring agents. For instance, it is not expected or obvious to apply or incorporate a phthalocyanine compound such as copper phthalocyanine in underwater applications, compositions, materials, or structures in which black color additives are used (e.g., which are intended to appear or remain black even after the addition of the phthalocyanine compound). Some embodiments in accordance with the present disclosure are directed toward compositions, materials, structures, or objects that include one or more pigments or coloring agents other than or exclusive of a phthalocyanine compound (e.g., copper phthalocyanine) for color establishment, determination, or adjustment purposes; and at least one phthalocyanine compound in an amount sufficient to provide boring bivalve resistive properties, secondary to or regardless, independent, or exclusive of color properties or a resulting color that the phthalocyanine compound(s) can provide.

In a number of embodiments in accordance with the present disclosure, a predetermined concentration of a phthalocyanine pigment, for instance, copper phthalocyanine, is at least 0.01 parts per hundred resin (phr). In multiple embodiments, a predetermined concentration of phthalocyanine pigment, more particularly copper phthalocyanine, is 0.05-0.5 phr. In a representative embodiment, a predetermined concentration of phthalocyanine pigment, more particularly copper phthalocyanine, is 0.1 phr.

A concentration of phthalocyanine pigment can be adjusted depending upon embodiment details, an underwater application or environment under consideration, or the availability or selection of one or more types of phthalocyanine pigments. For instance, in embodiments in which more than one phthalocyanine pigment is used, 0.05 phr of copper phthalocyanine can be used in combination with 0.05 phr of zinc phthalocyanine in order to provide boring bivalve resistance. Moreover, numerous modifications of phthalocyanine pigment(s) exhibiting variations in crystal structure and/or stability (for instance, stabilized alpha, unstabilized alpha, beta, epsilon, and chlorinated phthalocyanine pigment) can be included in a composition in accordance with the present disclosure.

As further detailed below, in certain embodiments in accordance with the present disclosure, a polymer formulation or composition can additionally include in addition to a phthalocyanine compound one or more other compounds at concentrations sufficient to act as marine borer resistive agents or counteragents. Such other compounds can be referred to as additional or adjunctive marine borer resistive agents, and can include, for instance, tin maleate, ammonium molybdenate, Chimasorb, Crodamide ER, silver zeolite, or another compound.

A polymer formulation or composition according to the present disclosure can be further combined, added, mixed, compounded, or impregnated with one or more additives or carriers. Examples of such additives include, but are not limited to, primary antioxidants, secondary antioxidants, Ca/Za stearates or other metal stearates, organic acid scavengers, inorganic acid scavengers, processing aids, stabilizers (e.g., UV or thermal stabilizers), UV absorbers, and color additives or color pigments such as carbon black. In some instances, one additive can serve at multiple functions (for example, carbon black at a concentration above 2.3 phr can serve as both colorant and UV stabilizer).

Particular embodiments of polymer formulations or compositions in accordance with the present disclosure can resist or prevent bivalve borer attack or damage (e.g., structural artifacts, defects, or damage) for at least 9, 12, or 24 months. Depending upon an underwater environment under consideration, a polymer formulation or composition in accordance with an embodiment of the present disclosure can resist or prevent bivalve borer (e.g., Martesia Striata) attack for at least 9 months. In some embodiments, a polymer formulation or composition provided by the present disclosure can resist or prevent bivalve borer damage for at least 12 months. In a number of embodiments, a polymer formulation or composition according to the present disclosure can dramatically reduce or prevent structural damage facilitated or caused by boring bivalves for at least 24 months. Certain embodiments in accordance with the present disclosure can resist or prevent bivalve borer attack or damage for the duration of a service lifetime (e.g., between 1 - 10 or more years) of a material, structure, or object having a surface that is exposed or exposable to a liquid environment (e.g., an external liquid, marine, or underwater environment, and/or an inner or internal environment in which a liquid is present) in which boring bivalves are expected or known to exist.

Representative Aspects of a Process for Producing a Marine Borer Resistive Article

FIG. 1 shows a flowchart of a process 100 for preparing, producing, or manufacturing and using a composition and/or article that is resistant to one or more types of marine borers (e.g., bivalve borers) according to an embodiment of the present disclosure. In a first process portion 110, a quantity or amount of at least one base polymer or plastic substance, compound, material, or resin is provided. Depending upon a target final product and application, a base polymer can be selected from a polymer including, based upon, or corresponding to at least one of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), acrylonitrile butadiene styrene (ABS), polystyrene (PS), polycarbonate (PC), polyamide (PA), and another polymer. In a number of embodiments, a base polymer includes or is polyolefin. In a representative embodiment, a base polymer or resin includes or is high density polyethylene (HDPE).

In a second process portion 120, at least one phthalocyanine compound or pigment is provided at a predetermined concentration relative to the base polymer(s), where the predetermined concentration is a concentration or quantity sufficient to at least inhibit marine borer attack upon the base polymer. Thus, the second process portion 120 involves providing at least one phthalocyanine compound at a concentration sufficient to act as a marine borer resistive agent or counteragent.

A phthalocyanine compound or pigment at a predetermined concentration can be selected from at least one of copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, and nickel phthalocyanine. Phthalocyanine compound concentration can be selected, adjusted, altered, or varied depending upon embodiment details or an intended application. In multiple embodiments, when the phthalocyanine compound includes or is copper phthalocyanine, the concentration of copper phthalocyanine is between 0.05-0.5 phr. In a representative embodiment, the concentration of copper phthalocyanine is selected at 0.1 phr.

An optional third process portion 130 involves providing one or more additional or adjunctive marine borer resistive compounds at quantities or concentrations sufficient to act as marine borer resistive agents or counteragents. A fourth process portion 140 involves providing one or more other substances or additives such as reagents, antioxidants, stabilizers, carriers, or colorants (e.g., relative to the amount(s) of base polymer(s) provided in association with the first process portion 110) in accordance with a target application, deployment environment, and/or market need under consideration. Examples of such additives include primary antioxidants, secondary antioxidants, Ca/Za stearates or other metal stearate, organic acid scavengers, inorganic acid scavengers, processing aids, thermal stabilizers, UV stabilizers, UV absorbers, color additives or pigments (e.g., carbon black). In a number of embodiments, a set of colorants provided in association with the fourth process portion 140 can serve as a set of principal colorants intended to provide a polymer - phthalocyanine composition in accordance with an embodiment of the present disclosure or an article manufactured therefrom with a target or final appearance or color that dominates or obscures coloration provided by the presence of a phthalocyanine compound.

The amount, quantity, and/or concentration of one or more additives can be determined or adjusted according to embodiment details, target application, deployment environment, or market need. In a representative embodiment, a generally black polymer composition, structure, object, or surface intended for marine applications includes carbon black as a black color additive and/or a UV absorber at a concentration of 2.5% as an additive, in combination with copper phthalocyanine at a concentration of 0.1 phr in order to effectively reduce, inhibit, or prevent damage caused by marine borers. In a fifth process portion 150, the selected base polymer(s), the phthalocyanine compound(s) or pigment(s), any additional or adjunctive marine borer resistive agent(s), and any additive(s) are contacted, combined, mixed, or blended to produce a resultant polymer - phthalocyanine compound combination, mixture, or blend. An order or sequence in which one or more (a) base polymers; (b) phthalocyanine pigments; (c) additional or adjunctive marine borer resistive agents; and/or (d) additives are contacted, combined, mixed, or blended can vary depending upon embodiment details. In some embodiments, the fifth process portion 150 involves introducing the selected base polymer(s) and the phthalocyanine compound(s), and possibly other constituents such as an additional or adjunctive marine borer resistive agent and/or one or more additives, into a machine or apparatus such as an extruder (e.g., a single or twin screw extruder). For instance, the base polymer(s), the phthalocyanine compound(s), an additional or adjunctive marine borer resistive agent, and one or more additives can be incorporated, combined, blended, and/or mixed together (e.g., to form a homogeneous or substantially homogeneous blend) under a specified temperature and configuration (e.g. rpm, speed) in a compounding machine.

In a sixth process portion 140, a resultant polymer - phthalocyanine compound mixture is formed or shaped (e.g., by way of a process involving a mold or template) into one or more types of structures, articles, objects, or surfaces. In a number of embodiments, a resultant polymer - phthalocyanine compound mixture can be shaped into one or more portions of pipes, rods, sheets, containers, tanks, chambers vessels (e.g., boats), swimmers, buoys, conduits, channels, casings, sleeves, shutterings, or support members. Furthermore, a resultant polymer - phthalocyanine compound mixture can be formed as or shaped into one or more portions of fibers or filaments such as ropes, webbing, fabric, textiles, or other types of flexible, semi-rigid, or non-rigid materials such as coatings, windows (e.g., a polyacrylate based window), or resins. A shape of a final article can be determined or selected based upon application or usage. In a representative embodiment, a resultant polymer- phthalocyanine compound mixture is carried by or forms the outer and/or inner surface(s) of one or more pipes, for instance, by way of a pipe extrusion process or technique, where such pipes are intended for exposure to or use in a liquid or aquatic environment in which marine borers are present or expected to be present.

A seventh process portion 170 involves deploying and/or using a marine borer resistant structure, article, object, or surface in accordance with an embodiment of the present disclosure in an aquatic environment in which the structure, article, object, or surface is exposable or exposed to marine borers such as Martesia Striata. In some embodiments, the seventh process portion 170 involves installing portions of an underwater structure such as piping system in a marine borer environment or habitat, where portions of the piping system that are exposable to marine borers (e.g., exterior, outer, and/or interior portions depending upon application) carry or include a polymer - phthalocyanine compound mixture in accordance with an embodiment of the present disclosure. The seventh process portion 170 can additionally or alternatively involve using an underwater structure while the structure is deployed in the marine borer environment, for instance, for carrying, conveying, or transporting a substance such as a chemical composition (e.g., which is extracted or used in association with a refining or manufacturing process); a substance or product intended for human or animal ingestion (e.g, a beverage such as drinking water; food; or a pharmaceutical substance); or a substance or product intended for human or animal body external application (e.g., a cosmetic substance); a substance intended for agricultural use; or a waste product (e.g., human or animal waste).

In certain embodiments, the seventh process portion 170 can further involve offloading or diverting a substance carried by a structure (e.g., a pipe) that includes a polymer - phthalocyanine compound mixture in accordance with an embodiment of the present disclosure toward, to, into, and/or through one or more other structures (e.g., another pipe, a container or tank, or a storage facility, one or more of which can be aquatic or land-based) that can include or exclude a polymer - phthalocyanine compound mixture in accordance with an embodiment of the present disclosure. The following representative example describes an experiment detailing particular aspects of a polymer composition provided in accordance with the present disclosure. One of ordinary skill in the art will understand that the scope of the present disclosure is not limited by the following representative example.

EXAMPLE ONE

An experiment in example one was conducted to evaluate an efficiency of copper phthalocyanine incorporated into base high density polyethylene (HDPE) for preventing, resisting, or delaying damage caused by bivalve boring larvae when such HDPE specimens were submerged underwater.

In the experiments of example one, specimens of HDPE polymer were prepared and categorized into 7 groups, namely group 1 to group 7. There were three specimens in each group. Each group was prepared as follows:

Group 1 : Control group. 100% HDPE resin with calcium stearate at a concentration or quantity of 0.2 phr (part per hundred), Irganox B215 (stabilizer) at a quantity of 0.2 phr, Irganox 1010 (antioxidant) at a concentration of 0.1 phr, and carbon black at a concentration of 2.3%.

Group 2: 100% HDPE resin with calcium stearate at a concentration or quantity of 0.2 phr (part per hundred), B215 at a quantity of 0.2 phr, Irganox 1010 at a concentration of 0.1 phr, carbon black at a concentration of 2.3%, and an inorganic silver zeolite (e.g., Irgaguard B5000) at a concentration of 0.3 phr.

Group 3: 100% HDPE resin with calcium stearate at a concentration or quantity of 0.2 phr (part per hundred), B215 at a quantity of 0.2 phr, Irganox 1010 at a concentration of 0.1 phr, carbon black at a concentration of 2.3%, and copper phthalocyanine at a concentration of 0.1 phr. Group 4: 100% HDPE resin with calcium stearate at a concentration or quantity of 0.2 phr (part per hundred), B215 at a quantity of 0.2 phr, Irganox 1010 at a concentration of 0.1 phr, carbon black at a concentration of 2.3%, and tin maleate at a concentration of 0.5 phr. Group 5: 100% HDPE resin with calcium stearate at a concentration or quantity of 0.2 phr (part per hundred), B215 at a quantity of 0.2 phr, Irganox 1010 at a concentration of 0.1 phr, carbon black at a concentration of 2.3%, and Chimasorb at a concentration of 0.05 phr.

Group 6: 100% HDPE resin with calcium stearate at a concentration or quantity of 0.2 phr (part per hundred), B215 at a quantity of 0.2 phr, Irganox 1010 at a concentration of 0.1 phr, carbon black at a concentration of 2.3%, and Crodamide ER at a concentration of 1%.

Group 7: 100% HDPE resin with calcium stearate at a concentration or quantity of 0.2 phr (part per hundred), B215 at a quantity of 0.2 phr, Irganox 1010 at a concentration of 0.1 phr, carbon black at a concentration of 2.3%, and ammonium molybdate at a concentration of 0.1 phr.

All specimens of HDPE polymer according to above-described recipes in each group were compounded by using a twin screw extruder and prepared by a compression molding technique to obtain test specimen sheets with a size of 1 1.5 x 22.5 x 1 centimeter under specified molding and cooling condition per below;

Compression temperature: 190 °C

Preheating time: 15 minutes

Compression time: 30 minutes

Pressure: 175 KN

Cooling rate: 1) 190 °C to 80 °C = 12.5 °C/ minute

2) 80 °C to 35 °C = 1.8 °C/ minute Test specimens of each group were placed, immersed, or submerged in an aquatic environment in which boring bivalves are known to exist for a period or nine months. Upon 9 months remaining submerged underwater, the test specimens of each group were collected, cleaned using a water jet, and observed or analyzed for determining numbers and/or dimensions of bore holes appearing in each specimen. Numbers of bore holes were recorded as set forth in Table 1.

Table 1: Numbers of bore holes caused by Pholadid bivalve in test specimens

Notes:

a = Numbers "x,y" represent bore holes on each side of test plates or test specimens b = Total number of bore holes recorded

Results

Table 1 shows numbers of bore holes appearing on each side of test plates or test specimens and total number of bore holes. After 9 months residing underwater, small bore holes from 1 to 4 millimeter in diameter were observed in the test specimens of Group 1, 2, 4, 5, 6, and 7. For instance, the number of small bore holes found on each side of Group 1 (i.e., base HDPE) test specimens replicates 1, 2, and 3 were 1,0; 4,2; and 5,2, respectively, where the numbers of bore holes corresponding to a first side and a second side of any given test specimen replicate are separated by a comma. Strikingly, there were no bore holes observed for the test specimens of Group 3. More specifically, no bore holes drilled by boring bivalve organisms were observed when the HDPE test specimens included copper phthalocyanine at a concentration of 0.1 phr. The results provided by example one indicate that copper phthalocyanine incorporated into polymers such as HDPE can entirely prevent, inhibit, resist, or delay damage caused by boring bivalves. Conclusions

The results of example one indicate that the incorporation of copper phthalocyanine into a set of base polymers (e.g., HDPE base polymer) at an appropriate concentration or quantity (e.g., 0.1 phr) relative to a quantity or amount of base polymer(s) under consideration can effectively prevent, resist, or delay damage caused by boring bivalves.

The results of example one additionally indicate that the inclusion of an appropriate relative concentration or quantity of (a) copper phthalocyanine as a primary boring bivalve resistive agent or counteragent; plus (b) one or more additional or adjunctive compounds such as a silver zeolite, tin maleate, Chimasorb, Crodamide ER, ammonium molybdenate, or another compound as a secondary, associated, or adjunctive boring bivalve resistive agent or counteragent can further enhance an extent to which a polymer composition in accordance with an embodiment of the present disclosure or an article made therefrom is resistant to one or more types of marine borers (e.g., boring bivalves such as Martesia Striata).

Particular embodiments of the disclosure are described above for providing novel, inventive, advantageous, and/or enhanced polymer material compositions for preventing, resisting, withstanding, or delaying damage caused by bivalve boring larvae during usage of the polymer in a liquid or aquatic environment (e.g., marine or submarine applications in which a polymer composition in accordance with an embodiment of the present disclosure forms an outer and/or an inner surface of an object, material, or substance that is exposable or exposed to the liquid or aquatic environment). While features, functions, compositions, applications, techniques, advantages, and alternatives associated with certain embodiments have been described within the context of those embodiments, other embodiments may also exhibit such advantages, and not all embodiments need necessarily exhibit such advantages to fall within the scope of the disclosure. It will be appreciated that several of the above-disclosed features, functions, compositions, applications, techniques, advantages, and alternatives thereof, may be desirably combined into other compositions or applications. The above-disclosed features, functions, compositions, applications, techniques, advantages, and alternatives thereof, as well as various presently unforeseen or unanticipated alternatives, modifications, variations or improvements thereto that may be subsequently made by one of ordinary skill in the art, are encompassed by the following claims.

Claims

1. A marine borer resistant composition comprising:

a set of base polymers intended for exposure to aliquid environment in which marine borers are expected to exist; and

a phthalocyanine compound at a predetermined concentration relative to the set of base polymers sufficient for at least substantially reducing a likelihood of marine borer intrusion into the set of base polymers.

2. The composition according to claim 1, wherein the phthalocyanine compound includes one of copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, and nickel phthalocyanine.

3. The composition according to claim 1, wherein the phthalocyanine compound is copper phthalocyanine.

4. The composition according to claim 1, wherein the phthalocyanine compound includes copper phthalocyanine at a concentration of at least approximately 0.01 phr. 5. The composition according to claim 4, wherein the concentration of copper phthalocyanine is between approximately 0.05 and approximately 0.

5 phr.

6. The composition according to claim 4 wherein the concentration of copper phthalocyanine is approximately 0.1 phr.

7. The composition according to claim 1 wherein the set of base polymers includes one of PE, PP, PVC, ABS, PS, PC and PA.

8. The composition according to claim 1 wherein the composition prevents intrusion of marine borers therein for at least approximately 12 months.

9. The composition according to claim 1, wherein the composition is one of a Martesia Striata resistive agent and a Martesia Striata counteragent.

10. The composition according to claim 1, wherein the composition is carried by a portion of one of a structure, a support member, a piping system, a receptacle, a flotation device, a textile, a rope, a fiber, and a filament that is exposable to the liquid environment.

1 1. The composition according to claim 1, further comprising an adjunctive compound at a predetermined concentration relative to the set of base polymers sufficient for at least substantially reducing a likelihood of marine borer intrusion into the set of base polymers.

12. A method for producing an article intended for exposure to a liquid environment in which marine borers are expected to exist, comprising:

providing a set of base polymers intended for immersion in the liquid environment; and

providing a phthalocyanine compound at a predetermined concentration relative to the set of base polymers, the phthalocyanine compound sufficient to at least substantially reduce a likelihood of marine borer intrusion into the set of base polymers;

combining the set of base polymers and the phthalocyanine compound; and forming an article having a surface that includes the set of base polymers and the phthalocyanine compound, the surface of the article intended for exposed to the liquid environment.

13. The method according to claim 12, wherein the phthalocyanine compound is one of copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, and nickel phthalocyanine.

14. The method according to claim 12, wherein the phthalocyanine compound is copper phthalocyanine.

15. The method according to claim 14, wherein the concentration of copper phthalocyanine is at least approximately 0.01 phr.

16. The method according to claim 14, wherein the concentration of copperphthalocyanine is between approximately 0.05 and 0.5 phr.

17. The method according to claim 14, wherein the concentration of copperphthalocyanine is approximately 0.1 phr.

18. The method according to claim 12, wherein said base polymer is one of PE, PP, PVC, ABS, PS, PC and PA.

19. The method according to claim 12, wherein combining the set of base polymers and the phthalocyanine compound comprises mixing the set of base polymers and phthalocyanine compound using a compounding apparatus.

20. The method according to claim 12, wherein the article is a portion of one of a pipe, a rod, a sheet, a container, a tank, a boat, a swimmer, a buoy, a support structure, a sleeve, a window, a rope, a fiber, and a filament.

21. The method according to claim 12, wherein the article comprises a structure for transporting one of a substance intended for human or animal ingestion, a substance intended for human or animal external application, a substance intended for agricultural use, and a waste product.

22. A marine borer resistant composition comprising:

a set of carrier materials intended for exposure to a liquid environment in which marine borers are expected to exist; and

a phthalocyanine compound at a predetermined concentration relative to the set of carrier materials sufficient for at least substantially reducing a likelihood of marine borer intrusion into the set of carrier materials.

23. The composition of claim 22, wherein the set of carrier materials is non-polymeric.