WO2005007279A2 - Composes servant a modifier les proprietes physiques de la glace et leurs procedes d'utilisation - Google Patents

Composes servant a modifier les proprietes physiques de la glace et leurs procedes d'utilisation Download PDF

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Publication number
WO2005007279A2
WO2005007279A2 PCT/US2004/022086 US2004022086W WO2005007279A2 WO 2005007279 A2 WO2005007279 A2 WO 2005007279A2 US 2004022086 W US2004022086 W US 2004022086W WO 2005007279 A2 WO2005007279 A2 WO 2005007279A2
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Prior art keywords
ice
hydrocolloid
water
tensile strength
eps
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PCT/US2004/022086
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English (en)
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WO2005007279A3 (fr
Inventor
Hajo Eicken
Christopher Krembs
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University Of Alaska Fairbanks
University Of Washington
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Publication of WO2005007279A2 publication Critical patent/WO2005007279A2/fr
Publication of WO2005007279A3 publication Critical patent/WO2005007279A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C09K3/185—Thawing materials

Definitions

  • 4,426,409 to Roe discloses the use of a cationic polymer (gelatin or ammonium-based compounds) to enhance the retention of freezing-point depressants within an aggregation of coal particles at low temperatures.
  • a cationic polymer gelatin or ammonium-based compounds
  • This technology does not rely on implicit properties of organic polymers in reducing macroscopic ice strength but rather uses polymers to reduce wash-out of water soluble freezing-point depressants.
  • its application is limited to coal with moisture contents typically ⁇ 5 %.
  • the embodiments described herein have not been previously considered and have a significant impact on ice microstructure and properties. Additionally, the microphysical principles underlying these effects have not been considered previously in this context and differ principally from those identified in previous research.
  • Figure 1 shows a schematic depiction of the deployment and distribution of a hydrocolloid emulsion in an application to reduce ice strength and stresses upon vessels, pilings and port installations.
  • Figure 2 shows the bulk ice salinity as a function of Xanthan gum concentration in parent water. Asterisks and solid dots denote first and second batch of experiments under different environmental conditions (growth rates). Nertical bars indicate the standard deviation of bulk salinities between three replicate samples.
  • Figure 2B shows the effective segregation coefficient k eff determined from experiments summarized in Figure 2A.
  • Figure 3 shows the segregation coefficient k eff vs. ice growth rate for different experiments.
  • FIG. 4 shows the pore microstructure of ice grown at different XG concentrations (A: 0 g I "1 , B: 0.01 g I "1 , C: 0.1 g T 1 , D: 0.5 g F 1 ).
  • the horizontal thin sections are 50 mm wide and were obtained at approximately 9 cm depth in the ice cover. They show the in situ pore distribution as evident from injection of a white contrast agent into pores. Ice salinities for the corresponding layers are A: 8.1 %o, B: 8.2 %o, C: 11.7 %>, D: 19.4 %o.
  • Figure 5 shows microphotographs of pore microstructure of ice identical to that in Figure 4 but lacking contrast agent. (A: 0 g F 1 , B: 0.01 g F 1 , C: 0.1 g F 1 , D: 0.5 g 1 _1 ).
  • the horizontal micrographs are 0.235 mm wide and were obtained at approximately 9 cm depth in the ice cover.
  • FIG. 6 depicts a demonstration of ductile failure and low yield strength of ice grown from water with XG concentration of 0.5 g 1 ⁇ (ice temperature -4.6 to -6.2 °C). Originally intact ice (A) completely disintegrates upon effortless kneading by hand (B). Figure 6C illustrates reduction in ice tensile strength ⁇ due to increase in porosity. Figure 7 shows ice grown from deionized water containing 0, 0.5 and 1 g/1 Xanthan gum (left to right).
  • Figure 8 shows the vertical thin section of freshwater ice containing no Xanthan gum, photographed in plain transmitted light (left) and between crossed polarizers (right).
  • Figure 9 shows the vertical thin section of freshwater ice grown from a 0.1 g/1 Xanthan gum solution, photographed in plain transmitted light (left) and between crossed polarizers (right).
  • Figure 10 shows the vertical thin section of freshwater ice grown from a 1.0 g/1 Xanthan gum solution, photographed in plain transmitted light (left) and between crossed polarizers (right).
  • Figure 11 shows the effective in situ permeability of sea ice containing variable Xanthan gum concentrations frozen at -20 °C from Xanthan gum solutions and saltwater of a salinity of 30 ppt.
  • Figure 12 shows the functional relationship between Xanthan gum solutions in water prior to freezing and the resulting effect on bulk salinity (ion retention) in the ice.
  • Figure 13 shows the effect of Xanthan gum on ion retention. Illustrated is the ratio of Xanthan gum to salinity in the water below the ice and the resulting deviation of the respective ratio in the resulting grown ice samples.
  • FIG. 15 shows images of horizontal ice thin sections from the 5 -cm ice horizon stained with contrast titanium dioxide and sea ice containing only sea salt (A) and EPS from Melosira arctica (B). The width of the images are 20mm. Microphotographs of unstained horizontal thin sections of the same ice of (A) and (B) illustrating the different structure in brine inclusions between the ice samples are shown.
  • Intra- (A.l) and inter- crystalline brine pores (A.2) in the control are absent in ice grown from culture water of Melosira arctica (B. 1-2).
  • the width of the microscopic images is 324 ⁇ m. Images of horizontal ice thin sections from the 5-cm ice horizon of sea ice containing only sea salt (C) and Xanthan gum lOmg L "1 (D). The widths are identical to those in Figures 15A and B.
  • Figure 16 shows the functional relation between EPS concentration in the water (A) and in the ice (B) and the resulting bulk salinity of the ice sheet. A.
  • Figure 17 shows the vertical profiles of particulate and dissolved organic material in the lower 10 cm of fast ice collected off the coast of Barrow.
  • (A) is the vertical profile of pigments Chi a ( ⁇ ) and Pheophytin (D) including their respective ratio to one another (o);
  • (b) is the vertical profiles of particulate nitrogen ( ⁇ ) and the ratio of carbon to nitrogen in particles >0J ⁇ m ( ⁇ );
  • (c) is the vertical profile of pEPS measured with the methods PSA (D) and AB ( ⁇ ) and their relation to POC (D); and
  • (d) is the vertical profile of dEPS measured with the method PSA (D) and the fraction of pEPS of total EPS (D).
  • Figure 18 shows a schematic summary of significant correlations of environmental variables (Ammonia NI-U; Nitrate NO 3 ; Nitrogendioxyde NO 2 ; Phosphaet PO 4 ; total dissolved nitrogen TDN; Silicate SI(OH) 4 ; Phaeophytin Pheo; Chlorophyll a Chi ⁇ ; total EPS tEPS; dissolved EPS dEPS; particulate organic carbon POC; carbon and nitrogen elementary composition of filtered particulate material p C/N) in the melted 1.8 cm vertically resolved ice-core sections of the lower 10 cm of Chukchi Sea ice using Spearman rank correlation. Lines represent significant correlations (positive correlations solid, negative correlations dashed) included are correlation coefficients followed by significance levels.
  • environmental variables Ammonia NI-U; Nitrate NO 3 ; Nitrogendioxyde NO 2 ; Phosphaet PO 4 ; total dissolved nitrogen TDN; Silicate SI(OH) 4 ; Phaeophytin Phe
  • Figure 19 shows the mass molecular fractions of total EPS precipitated in ethanol and separated via differences in density in a NaCl and CsCl gradient.
  • the black line represents averaged concentrations per collected sample fractions of three parallel runs, included in gray are standard deviation.
  • Concentrations of EPS are given in absorption of light 490nm of the Phenol-Sulfur-glucose complex of prior hydrolyzed macromolecules.
  • Figure 20a shows the frequency distribution of pore cross sectional areas for sea ice collected in sea ice of Elson Lagoon 2001(D) and the Chukchi Sea ( ⁇ ) and artificial sea ice containing only sea salt (O) and water of a culture of Melosira arctica (0) (pores analyzed, n>700).
  • Figure 20b shows the frequency distribution of surface to area ratios of crosses sectional images of the same ice.
  • a hydrocolloid includes mixtures of two or more such compounds, and the like.
  • “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.
  • the phrase “optionally contains an additive” means that an additive can or cannot be present.
  • Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect 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 aspect.
  • contacting is meant an instance of exposure by close physical contact of at least one substance to another substance.
  • sufficient amount is the amount needed to achieve the desired result or results.
  • Disclosed are compounds, compositions, and components that can be used for, can be used in conjunction with, can be used in preparation for, or are products of the disclosed methods and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein.
  • hydrocolloids and other additives are disclosed and discussed, each and every combination and permutation of the hydrocolloid and additive are specifically contemplated unless specifically indicated to the contrary.
  • A-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated.
  • each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • any subset or combination of these is also specifically contemplated and disclosed.
  • the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions.
  • steps in methods of making and using the disclosed compositions are if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
  • hydrocolloids can be used to change the physical properties of ice.
  • hydrocolloid as used herein is defined as hydrophilic polymers of vegetable, animal, microbial, or synthetic origin that contain one or more hydroxyl groups.
  • the hydrocolloid can be an exopolymer or a derivative thereof.
  • exopolymer as used herein is defined as an organic polymer secreted into the environment by a aquatic or terrestrial microorganism.
  • exopolymer also includes a capsule of the naturally-occurring polymer intimately associated with the cell surface of the microorganism.
  • exopolymer is also referred to as an exocellular polysaccharide or EPS.
  • the exopolymer can be a single polymer or a mixture of two or more polymers. When the exopolymer contains a mixture of two or more polymers, the polymers can possess different functional groups and/or molecular weight. Any of the exopolymers described herein can be chemically modified to produce a derivative of the naturally- occurring exopolymer. In one aspect, the exopolymer is produced from a microorganism from the kingdom protista or monera.
  • the microorganism when the microorganism is from the kingdom protista, can be from the phyla Acrasiomycota (cellular slime molds), Chrysophyta (golden algae), Euglenophyta (eugenoids), Rhizopoda (amoebas), Actinopoda , Chytridomycota (chytrids), Foraminifera (forams), Rhodophyta (red algae), Apicomplexa, Ciliophora (ciliated protozoans), Myxomycota (plasmodian slime molds), Zoomastigophora (zooflagellates), Bacillariophyta (diatoms), Dinoflagellata (dinoflagellates), Chlorophyta (green algae), Oomycota (water molds), Vaccinonada (archezoa), or Phaeophyta (brown algae).
  • phyla Acrasiomycota cellular slime molds
  • the microorganism when the microorganism is from the kingdom monera, the microorganism can be a cyanobacteria, an archaebacteria, a methanogen, an extreme halophile, a thermoacidophile, or an eubacteria.
  • the exopolymer is produced from a microalga, a microphyte, an unicellular alga, or an eubacteria.
  • the exopolymer is produced from the diatom Melosira arctica.
  • Melosira arctica is a filamentous diatom that commonly occurs within and below the Arctic ice pack and produces large amounts of exopolymers. Not wishing to be bound by theory, it is believed that Melosira arctica attaches to the underside of ice and forms meter-long chains.
  • the hydrocolloid can be the hydrocolloid comprises agar, arabinoxylan, carrageenan, carboxymethylcellulose, cellulose, curdlan, gelatin, gelan, ⁇ -glucan, guar gum, gum Arabic, locust bean gum, pectin, or starch.
  • the hydrocolloid can be algmic acid or the salt thereof.
  • Alginic acid is a polymer of mannuronic acid and guluronic acid, with the proportion of the two depending upon the type of brown algae. Alginic acid can be readily converted to the corresponding salt using techniques known in the art. Examples of alginates useful herein include, but are not limited to, sodium, potassium, or calcium alginate.
  • propylene glycol alginates are available from C.P. Kelco Company.
  • the acetylated alginates disclosed in U.S. Patent No. 5,444,160, which is incorporated by reference in its entirety, can be used herein.
  • the hydrocolloid can be Xanthan gum or a derivative thereof.
  • Xanthan gum is a heteropolysacchari.de of high molecular weight, composed of D-glucose, D-mannose and D-glucuronate moieties in a molar ratio of 2:2:1, respectively.
  • the Xanthan gum is produced by the bacterium Xanthomonas campestris, which compound and its preparation are fully described in U.S.
  • Xanthan gums that can be useful in the methods described herein can be obtained from other known Xanthomonas bacteria such as, for example, Xanthomonas carotate, Xanthomonas incanae, Xanthomonas begoniae, Xanthomonas malverum, Xanthomonas vesicatoria, Xanthomonas papavericola, Xanthomonas translucens, Xanthomonas vasculorum, and Zanthomonas hederae.
  • Xanthomonas bacteria such as, for example, Xanthomonas carotate, Xanthomonas incanae, Xanthomonas begoniae, Xanthomonas malverum, Xanthomonas vesicatoria, Xanthomonas papavericola, Xanthomonas translucens, Xanthomonas va
  • a derivative of a Xanthan gum includes, but is not limited to, non- pyruvylated, non-acetylated, and non-pyruvylated-non-acetylated Xanthan gums whether produced through fermentation of mutant strains of Xanthomonas or produced through chemical or enzymatic processes performed on conventional Xanthan gum or any combination thereof.
  • the derivative of the Xanthan gum can be prepared by fermentation of mutant strains of Xanthomonas campestris as described in U.S. Patent No. 5,514,791, the disclosure of which is incorporated herein by reference.
  • non-acetylated Xanthan gum may be prepared by chemical deacetylation of Xanthan gum produced by Xanthomonas campestris as described in U.S. Patent Nos. 3,000,790 and 3,054,689.
  • Alternative methods for generating derivatives of Xanthan gum are disclosed in U.S. Patent Nos. 6,432,155; 6,432,359; 4,713,449; and 5,772,912, which are incorporated by reference in their entireties. II. Methods of Use Any hydrocolloid described herein can be used to change the physical properties of ice.
  • the term "changed" as used herein is defined as increasing or decreasing a particular property of ice when contacted with one or more hydrocolloids when compared to ice that has not been contacted with the hydrocolloid(s).
  • Various physical properties of the ice can be changed with the use of a hydrocolloid, which will be discussed below.
  • the hydrocolloid can reduce the tensile strength of ice when compared to ice that has not been contacted with or formed from the hydrocolloid. By reducing the tensile strength of ice, the resultant ice is not as hard and can be further manipulated or handled, which will be discussed below.
  • ice produced from one or more hydrocolloid(s) has a tensile strength of 0.3, O.4., 0.5, 0.6, 0.7, 0.8., 0.9, 1.0 MPa (where any range can be formed from these values), or any combination endpoints lower than the tensile strength of ice that has not been contacted with or formed from the hydrocolloid.
  • the tensile strength of ice formed by or contacted with the hydrocolloid is 10% to 90%, 20% to 90%, 20% to 60%, 30% to 70%, or 30% to 60% lower than untreated ice.
  • the hydrocolloid can reduce tensile strength of ice by a number of different mechanisms.
  • the hydrocolloid when used to produce ice or is contacted with ice, the resulting ice is less permeable. This results in ice having a greater tendency of entrapping gasses and dissolved materials.
  • the ability of gasses and other dissolved materials such as, for example, inorganic ions, salts, dyes, and organic particles, to diffuse from the ice at the ice-water interface is reduced.
  • the salinity of ice treated with or formed by the hydrocolloid can be substantially higher (20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 150%, 200%, 300%, 400%, or 500%) than ice not formed from or contacted with the hydrocolloid.
  • the salinity of ice can also be expressed as a segregation coefficient, which is defined as the concentration of salt in the ice divided by the concentration of the salt in the bulk water.
  • the segregation coefficient of ice formed from or contacted with the hydrocolloid is from 0.2 to 0.95, 0.3 to 0.95, 0.4 to 0.95, 0.5 to 0.95, 0.6 to 0.95, 0.7 to 0.95, 0.8 to 0.95, or 0.9 to 0.95.
  • the morphology of the ice changes as well. Pore sizes of ice contacted with or formed by the hydrocolloid are significantly higher than pore sizes of untreated ice.
  • the pore sizes in treated ice are 10%, 20%, 30%, 40%, 50%, 75%, 100%, 125%, 150%, 200%, 300%, 400%, or 500% greater than the pore size of ice not treated with the hydrocolloid.
  • the hydrocolloid can increase the viscosity of the brine, which can significantly reduce future desalination of the ice by the brine. Therefore, the more dissolved materials or gasses the ice can retain or the longer the dissolved materials or gasses are retained by the ice, the tensile strength of the ice can be reduced.
  • the hydrocolloids can facilitate the retention of dissolved materials and gasses in the ice, which ultimately reduces the tensile strength of the ice.
  • the ice can be contacted with the hydrocolloid using a variety of techniques. Examples of such techniques include spraying, dipping, coating, or brushing the ice with the hydrocolloid.
  • the hydrocolloid can be mixed with water prior to ice formation using techniques known in the art.
  • the water can be fresh water, saline water, or water that contains other dissolved materials that can be entrapped by the ice.
  • the hydrocolloid in the form of a foam or emulsion and used as an effective carrier of other components including, but not limited to, additives, stains, cryoprotectants, anti-fouling agents, anti-corrosion agents, and the like.
  • the amount of the hydrocolloid used will also vary depending upon the hydrocolloid that is selected, the type of water, and the environmental conditions. In one aspect, the amount of hydrocolloid that can be used is greater than 0.05 g/L of water.
  • the amount of the hydrocolloid is from 0.05 to 10g/L 5 0.05 to 9 g/L, 0.05 to 8 g/L, 0.05 to 7 g/L, 0.05 to 6 g/L, 0.05 to 5 g/L, 0.1 to 5 g/L, or 0.2 to 5 g/L.
  • hydrocolloids to change the physical properties of ice provides numerous advantages. First, hydrocolloids are commercially available or easily prepared and efficient at low concentrations at very low production costs (e.g., Xanthan gum is commercially available at prices of around $6.60 per kg).
  • the hydrocolloids are for the most part environmentally degradable at a rate slow enough to persist for months during the cold season but fast enough to prevent build-up during the warm season. Due to their general high viscosity, the hydrocolloid will not disperse or be diluted in the environment. Finally, the hydrocolloid has a tendency to adhere to or concentrate at surfaces where its impact is greatest. In one aspect, once the hydrocolloid is incorporated into the ice, the desired effect persists for long periods of time due to the greatly reduced desalination rates discussed above. Thus, there is no need for re-application of the hydrocolloid to the ice. Furthermore, the softened ice can still maintain (and even improve) its insulating properties with beneficial environmental and strategic effects.
  • hydrocolloids for changing the physical properties of ice.
  • the introduction of hydrocolloid into surface waters at the onset of fall freeze-up and during winter ice growth in cold region harbors or other marine installations can be performed.
  • Such a procedure would allow for operations in these waterways during the course of winter without restrictions or damage due to solid ice. It would furthermore significantly reduce or abate potential damage due to build-up of ice internal stresses that are known to cause substantial, recurring damage to structures in important waterways.
  • the hydrocolloid is Xanthan gum or a hydrocolloid produced from Melosira arctica.
  • the hydrocolloid does not prevent ice formation, which maintains the insulating properties of an ice cover (with better insulating properties due to entrainment of gas bubbles and reduced brine drainage).
  • heat loss from a water body is actually minimized, which reduces the total amount of ice formed while at the same time reduces moisture fluxes that would otherwise lead to fog and icing problems.
  • the application of the hydrocolloid would reduce ice strength while giving the appearance of port facilities being completely ice-locked.
  • the hydrocolloid is highly effective even at very low concentrations (e.g., ⁇ 1 g 1 _1 , as compared to, e.g., tens to hundreds of grams per liter for glycol- based freezing-point depressants).
  • the hydrocolloid can be deployed as an emulsification of seawater pumped in situ at the bottom or at mid-water level, mixed with air from an above-ground intake and dispensed through a rotating arm or series of mobile or fixed pipes ( Figure 1).
  • the air bubbles retained within the viscous fluid would induce the emulsion to float up under the ice and bring it into direct contact with the ice water interface, where its effect is strongest. Owing to the significant reduction in molecular diffusivities of gases and dissolved matter in such emulsified water, additives as well as air bubbles can be maintained at higher concentrations for significant periods of time. Furthermore, build-up of the hydrocolloid under the ice in the laminar boundary layer further minimizes loss due to turbulent shear and advection.
  • the large-scale application of the hydrocolloid at oil and gas terminal installations in seasonally or episodically ice-covered water can be deployed either through surface spraying prior to freeze-up or injection of bubble-emulsion from below using rotary or mobile dispenser units;
  • the small-scale deployment of the hydrocolloid along quays, pilings, in lock chambers, marinas and other installations to reduce or abate build-up of stress against installations due to ice growth and ice pressure can be performed;
  • the large-scale application of hydrocolloids in closed or semi-enclosed port basins, shipyard docks and other large marine enclosures, which will allow the passage of vessels without full or any ice-strengthening, can be utilized.
  • the article can be any article that is exposed to freezing temperatures and water, including, but not limited to, pipes, plumbing fixtures, airplanes, roadways, and the like.
  • the hydrocolloid can be used a de-icing agent.
  • the hydrocolloid can be used as a lubricant under cold conditions.
  • Xanthan gum can be used as a drilling fluid additive, which reduces strain to drill gear when drilling in cold, hard ground such as permafrost.
  • deployment of a hydrocolloid in combination with water/brine mixtures into ground surface or other semi-enclosed terrestrial structures can prevent or abate freeze-damage to buried or half buried structures in seasonally frozen or permafrost regions.
  • adding a slurry of the hydrocolloid such as, for example, Xanthan gum and water, where the salinity of the water corresponds to the in situ soil salinity can prevent freeze-damage of pipes and ensure access to buried structures even in the coldest part of the season while at the same time act as an in situ lubricant.
  • the hydrocolloid can be used as a refrigerant in a cooling system.
  • freon-based refrigerants The phasing out of freon-based refrigerants has resulted in an increasing market for environmentally inert and harmless alternative refrigerants.
  • One such technique widely employed is the use of ice-brine slurries for refrigeration applications ranging from food display cases in supermarkets to cooling of the railroad/car tunnel between the UK and France (Paul, 1993).
  • the efficiency of the brine-ice coolant and the applicable temperature range increases with increasing ice content and increasing salinity.
  • NaCl (and other inorganic salts) brines the minimum temperature that can be achieved is limited by the temperature at which the freezing-point depressant properties of the dissolved salt in the brine are overtaken by the tendency for salt to precipitate out of solution.
  • the reduction in strength of the ice slurry can be expected to greatly reduce or completely prevent the negative impacts of local freeze-up due to variations in temperature control (or allow for lower temperatures to be achieved in the coolant).
  • the rheological properties of the hydrocolloid (Groisman and Steinberg, 2001) concentrated in the remaining liquid will ease pumping and conveyance of the ice-liquid coolant.
  • the efficiency of the cooling system will be increased (and maintenance decreased) when the refrigerant contains one or more hydrocolloids. Any cooling system that requires the use of a refrigerant can be used herein.
  • a hydrocolloid can be used in the food and agricultural industry.
  • the hydrocolloid can be used in the softening and modification of frozen food, which can alter the color, taste, and nutrition of the frozen food.
  • frozen food e.g., by altering the crystal texture of ice, different forms of frozen food are contemplated (e.g., slurpee applications).
  • thermal and mechanical frost protection of agricultural produce can be achieved by spraying a composition of the hydrocolloid onto fruit and crops sensitive to freeze damage.
  • the hydrocolloid increases water retention on plants, reduces convective heat exchange, and reduces mechanical and dehydration damage from ice crystals present on the plant surface.
  • fish and poultry dip-freezing in chilled brine containing a hydrocolloid can be improved by achieving less dehydration of the meat while increasing chilling rate.
  • the hydrocolloid can be used to protect microbial species utilized in the food industry.
  • extracellular cryoprotection and osmotic stabilization of yeasts, lactobacteria, and consumable microalgae can be achieved by submerging the microbial species into a composition composed of water and a hydrocolloid and freezing the composition for storage and transportation.
  • described herein is a method for facilitating the removal of ice on an article, comprising contacting the article with a hydrocolloid prior to exposing the article to conditions that will promote ice formation on the article.
  • the frozen food prior to freezing, when a food article is contacted with a hydrocolloid, the frozen food is preserved better and protected from freeze damage. For example, increased surface preservation, reduced dehydration, reduced mechanical damage, reduced phase segregation, and better mechanical separation are possible when the food article is contacted with hydrocolloid.
  • the hydrocolloid can protect the appearance of fish frozen in brine solution before shipment. By reducing the adhesive forces between the frozen fish, the fish scales and skin remain undamaged by the freezing/storage process.
  • the hydrocolloid can be used to treat sewage. Microbial degradation of freshwater sewage at subzero temperatures is limited to a fraction of liquid water in the ice if sewage cannot be directly be pumped into the marine environment.
  • reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
  • Xanthum gum was purchased from Sigma Aldrich.
  • the exopolymer produced by Melosira arctica was obtained by growing cultures enriched with f/2 nutrient medium fortified with silicate to high densities in 1,000 L of water illuminated over 24 hours and sealed in polyethylene bags.
  • Example 1 Two sets of experiments were conducted by growing NaCl ice in four 200 1 insulated tanks placed outside in Feb/March 2002 with ambient temperatures ranging between about -30 and -5 °C conducted under natural environmental conditions at the University of Alaska in Fairbanks. Xanthan gum was added to three of these tanks in each experiment at concentrations of 0.01, 0.05, 0.1, 0.25, 0.5 and 1 g F 1 , and a control without any additive. A pressure relief mechanism prevented build-up of pressure within the tank during ice growth.
  • Ice thickness was measured twice daily and the experiment terminated after an ice thickness of approximately 0.15 m was reached within a week.
  • Three sets of replicate samples (10 x 10 cm in cross-section) were obtained from each tank and sectioned into 2.5 cm thick slices for measurements of salinity and XG concentration. Nertical and horizontal thin sections were cut and photographed as described by Eicken (1998).
  • An integral measure of the effect of Xanthan gum (XG) on ice growth and properties is shown in Figure 2a, which indicates the increase in bulk ice salinity as a function of XG concentration for a set of outdoor experiments. For XG concentrations of about 0.5 g 1 _1 (in the parent water mass), salinity of the ice is increased by more than a factor of two.
  • the values determined here range between about 0.24 and 0.85 at growth velocities of about 1 to 2.5 cm day -1 .
  • the segregation coefficient of 0.85 is the highest measured and reported so far ( Figures 2b and 3) for any type of saline ice grown under natural conditions. At the same time, it is at least twice as high as values typically found in natural sea ice under rapid growth conditions.
  • the in situ liquid (brine) pore volume fraction N t /V was derived according to the method described by Cox and Weeks (1983).
  • the brine porosity of ice grown from water with XG additive was higher by a factor of more than two.
  • this increase in porosity represents a conservative estimate because the method of computing in situ brine volumes does not account for the additional impact ofXG on the pore space.
  • differences in ice temperature due to different thickness also result in an underestimation of the increase in porosity under full-scale, natural conditions.
  • Example 2 In a pilot experiment, ice was grown in 1 1 containers from deio ized water with the addition of Xanthan gum at 0.5 and 1.0 1 g concentrations in two of these to assess impacts on ice properties.
  • Figure 7 shows the results of this experiment, demonstrating the substantial increase in gas bubble retention (and smaller bubble sizes) along with the formation of intragranular, lamellar inclusions of polymers.
  • Freshwater ice was grown from deionized water by placing 5 1 containers insulated at the sides and bottom and placed in an insulated larger container so as to only expose the water/ice surface in a cold room at ambient temperatures of -10 °C.
  • Example 3 To test the effect of Xanthan gum on sea ice permeability, sea ice was grown in 1 meter long 10 cm diameter laterally insulated pipes filled with salt water and Xanthan gum solutions from the surface. Sea ice was grown in a range of Xanthan gum between 0.01 to 1 g Xanthan gum L containing solutions at a salinity of 30 ppt. Hydraulic conductivity of the ice with the underlying water was used to determine the sea ice permeability at in situ temperatures and conditions. Results indicate that effective permeability of ice grown in Xanthan gum solutions is affected by one order of magnitude by Xanthan gum in a range between 0.001 tolg per liter.
  • Seawater salinity (30 ppt) enriched with EPS from Colwellia psychrerythraea displayed a statistically significant microbially induced increase in sea-ice bulk salinity, which was most prominent near the ice bottom and is similar to results obtained during the Melosira arctica experiment.
  • EPS concentrations in the water were 3.8 times higher than in the ice and similarly to observations in the Melosira arctica experiment at identical 2.5-5- cm ice horizon (only 1.06 factor difference). Results of this experiment showed that a natural marine bacterium can affect the properties of sea ice.
  • Bacterial culture Specific total EPS production rate Range temperature ( ⁇ g XGEQN r "1 )
  • Ice containing exclusively salt in comparison, displayed brine inclusions with defined ellipsoid shapes and structural orientation. Due to the large complexity of shapes a distinction between intra- and inter- crystalline brine pores seen in the control ice ( Figures 15A.1 and A2), it was impossible to discern in the presence of EPS from Melosira arctica ( Figures 15B.1-2). Similarities and differences in the effect of EPS on sea ice bulk salinity by two fundamentally different organism classes Several factors influence the way an exopolymer can change the properties of ice. Factors include, but are not limited to, EPS concentration, EPS composition and the rate of ice growth.
  • Slower freezing rates should result in a higher segregation coefficient for salt.
  • Minimum bulk salinities were higher in the ice being spiked with EPS from Melosira arctica (Figure 16b) and comparable to EPS concentration in other experiment. This result indicates a strong effect of Melosira arctica EPS, which is insufficiently resolved using integrated ice core measurements.
  • EPS from Melosira arctica has a high affinity for ice.
  • EPS in the particulate fraction was measured independently by two methods, the Phenol sulfuric acid method (PSA) and the Alcian blue dye-binding assay (AB).
  • PSA Phenol sulfuric acid method
  • AB Alcian blue dye-binding assay
  • dEPS concentration was measured and reached an average 8.1 x 10 "4 g C l "1 , SD 2.7 x 10 "4 g C l "1 . Concentrations did not vary significantly with depth. The concentration of dEPS was higher than that of pEPS, and was illustrated as a fraction of total EPS in Figure 17d. pEPS accounted on average for only 21.1% (SD 9.7) of the total EPS concentration and was independent of the distance from the ice water interface. The elementary composition of particulate organic material in carbon and nitrogen can be an indication of the relative freshness of the material assuming that growth limiting elements are remineralized at a faster rate.
  • the ratios of total dissolved nitrogen to phosphate is an indication of a relative shift in the Redfield ratio of cells and respective nutrient limitations of the system leading to nutrient regeneration. Ratios increased from 10.6 to 34.5 with distance from the interface, which indicates a relative limitation of available phosphate compounds. The degree of a microbially nutrient regenerated system is also indicated in the ratio of nitrate to total dissolved nitrogen. The opposite trend of the ratio with depth to that of the Redfield ratio indicates a qualitative transformation of dissolved oxygenated nitrogen compounds to reduced compounds in the bottom ice by the microbial community, which suggests pronounced heterotrophic activity.
  • Co ⁇ elations between paired variables illustrated a strong spatial dependence of the compounds of nitrogen, silicate, and photopigments with distance to the water interface.
  • the distinct shift from a nitrate (new production) to an ammonia dominated (microbially regenerated) system is again indicated in the predominantly positive correlation of nitrate with all variable partners and a predominantly negative correlation of ammonia with pigment concentrations and depth.
  • Phosphate in contrast, correlated only positively with particulate nitrogen, which can be an indicator of fresh particulate material.
  • % of the pores contained no air bubbles followed by 19.3 % of the pores filled with small air bubbles displacing 25% the brine by area. Pores completely filled with air were very rare and occurred in only 1.6%. Brine inclusions not filled with stained EPS (or not reached by stain) contained in 0.5% of the observed diatoms, and 2.9% detritus were in 27.0% very pointy in shape. Detritus concentrations were significantly higher than diatom concentrations in each of the pore categories, which is consistent with the low Chi a to Pheophytin ratio in melted ice cores supporting a senescent algal bloom. A clear increase in pointiness (53%) of pores was observed in brine inclusions that were filled to 100% with pEPS.
  • Area cover of Relative frequency Co-occurrence in same pore: inclusion by: air bubble pEPS diatoms detritus pointy pores
  • Example 5 Five different treatments were performed on 0.7 L Melosira arctica culture water samples to determine the molecular nature of the active substance affecting the physical properties of sea ice. Prior to freezing, samples from a Melosira arctica batch culture were treated according to the treatment scheme outlined in Table 4. To assure identical conditions, samples were placed in a thermo-insulated water bath 30 x 40 x 20 cm of a salinity of 33 ppt so that the water levels in the samples matched the water level of the surrounding water. Freezing of the samples and the surrounding water was induced from the surface in a cold room set to -10°C and continued for approx 24 hours.
  • Glycoprotein To knock out a potential glycoprotein, a denaturing buffer (0.5% SDS, 1% b- mercaptoethanol) was introduced to the sample and incubated for 10 min at 37 °C.
  • IX G7 Reaction Buffer 50 mM Sodium Phosphate (pH 7.5 @ 25°C)], supplemented with 1% NP-40, at 37°C was also added.
  • N-Glycosidase F also known as PNGase F (glycerol free)
  • PNGase F glycerol free
  • an amidase was added to the sample, which cleaves glycoproteins between the innermost GlcNAc and asparagine residues of high mannose, hybrid and complex oligosaccharides from N-linked glycoproteins.
  • a control for the increase in temperature to 37°C was introduced.
  • One additional heat treatment at 72 °C was performed to determine the sensitivity of the active agent to heat below 100°C.
  • Data were compared to known conditions: Melosira arctica culture water untreated (temperatures ⁇ 4°C) and a pure NaCl solution. Table 4. Treatment conditions and resulting effects on sea ice microstructural features qualitatively assessed on repetitive photomicrographs at 250 x magnification.

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Abstract

L'invention concerne des composés servant à modifier les propriétés physiques de la glace et leurs procédés d'utilisation.
PCT/US2004/022086 2003-07-10 2004-07-09 Composes servant a modifier les proprietes physiques de la glace et leurs procedes d'utilisation WO2005007279A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006086392A3 (fr) * 2005-02-07 2008-05-02 Envirotech Services Inc Compositions de deglaçage a faible viscosite
NO20065743L (no) * 2006-12-12 2008-06-13 Icemining Tech As Fremgangsmåte for oppstøtting av gruverom, tunnel eller hulrom i jorden ved bruk av is med modifisert flytehastighet
CN113569408A (zh) * 2021-07-28 2021-10-29 黄河水利委员会黄河水利科学研究院 一种河冰力学性能的代表性表征方法
CN116451511A (zh) * 2023-06-16 2023-07-18 中国人民解放军国防科技大学 基于roms模型的海冰数值仿真方法、装置及设备

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US4358389A (en) * 1980-10-25 1982-11-09 Hoechst Aktiengesellschaft Agent for de-icing and protecting against icing-up
US4388203A (en) * 1981-11-20 1983-06-14 The Dow Chemical Company Composition and method for melting frozen aqueous solutions
US4439337A (en) * 1981-11-20 1984-03-27 The Dow Chemical Company Composition and method for preventing freezing together of various surfaces
EP0437360A1 (fr) * 1990-01-11 1991-07-17 Warner-Lambert Company Agent volumique hydrocolloide et composition le contenant
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US6180562B1 (en) * 1999-01-20 2001-01-30 The Egg Factory, L.L.C. Compositions for protecting plants from frost and/or freeze and methods of application thereof
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US6368591B2 (en) * 1998-05-15 2002-04-09 Shanghai Sine Pharmaceutical Corporation Ltd. Beneficial microbe composition, new protective materials for the microbes, method to prepare the same and uses thereof

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US4117214A (en) * 1973-07-19 1978-09-26 The Dow Chemical Company Method and composition for reducing the strength of ice
US4358389A (en) * 1980-10-25 1982-11-09 Hoechst Aktiengesellschaft Agent for de-icing and protecting against icing-up
US4388203A (en) * 1981-11-20 1983-06-14 The Dow Chemical Company Composition and method for melting frozen aqueous solutions
US4439337A (en) * 1981-11-20 1984-03-27 The Dow Chemical Company Composition and method for preventing freezing together of various surfaces
EP0437360A1 (fr) * 1990-01-11 1991-07-17 Warner-Lambert Company Agent volumique hydrocolloide et composition le contenant
US5261241A (en) * 1991-02-08 1993-11-16 Japan Pionics Co., Ltd. Refrigerant
US6183664B1 (en) * 1997-04-24 2001-02-06 Ki-Bum Kim Deicing and snow-removing composition, method for producing the same, and use thereof
US6368591B2 (en) * 1998-05-15 2002-04-09 Shanghai Sine Pharmaceutical Corporation Ltd. Beneficial microbe composition, new protective materials for the microbes, method to prepare the same and uses thereof
US6180562B1 (en) * 1999-01-20 2001-01-30 The Egg Factory, L.L.C. Compositions for protecting plants from frost and/or freeze and methods of application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006086392A3 (fr) * 2005-02-07 2008-05-02 Envirotech Services Inc Compositions de deglaçage a faible viscosite
US7632421B2 (en) 2005-02-07 2009-12-15 Envirotech Services, Inc. Low viscosity de-icing compositions
NO20065743L (no) * 2006-12-12 2008-06-13 Icemining Tech As Fremgangsmåte for oppstøtting av gruverom, tunnel eller hulrom i jorden ved bruk av is med modifisert flytehastighet
CN113569408A (zh) * 2021-07-28 2021-10-29 黄河水利委员会黄河水利科学研究院 一种河冰力学性能的代表性表征方法
CN113569408B (zh) * 2021-07-28 2024-02-20 黄河水利委员会黄河水利科学研究院 一种河冰力学性能的代表性表征方法
CN116451511A (zh) * 2023-06-16 2023-07-18 中国人民解放军国防科技大学 基于roms模型的海冰数值仿真方法、装置及设备
CN116451511B (zh) * 2023-06-16 2023-08-22 中国人民解放军国防科技大学 基于roms模型的海冰数值仿真方法、装置及设备

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