EP1238038A1 - Compositions degivrantes et antigivrantes ecologiques - Google Patents

Compositions degivrantes et antigivrantes ecologiques

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Publication number
EP1238038A1
EP1238038A1 EP00973654A EP00973654A EP1238038A1 EP 1238038 A1 EP1238038 A1 EP 1238038A1 EP 00973654 A EP00973654 A EP 00973654A EP 00973654 A EP00973654 A EP 00973654A EP 1238038 A1 EP1238038 A1 EP 1238038A1
Authority
EP
European Patent Office
Prior art keywords
fpd
biodegradable
surfactant
toxic
freezing point
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00973654A
Other languages
German (de)
English (en)
Other versions
EP1238038A4 (fr
Inventor
Carolyn S. Westmark
Kevin G. Joback
Marina Temchenko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vencore Services and Solutions Inc
Original Assignee
Foster Miller Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foster Miller Inc filed Critical Foster Miller Inc
Publication of EP1238038A1 publication Critical patent/EP1238038A1/fr
Publication of EP1238038A4 publication Critical patent/EP1238038A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes

Definitions

  • the present invention relates to methods and compositions for de- icing and anti-icing surfaces, especially aircraft surfaces, in which the compositions have a tailorable rate of degradation.
  • Safe operation of commercial and military aircraft during icing conditions requires the removal of ice and frozen deposits from critical surfaces prior to takeoff.
  • Military aircraft especially must be capable of safely conducting operations in adverse winter weather if required by the mission.
  • Mission specific readiness requirements and long intervals between successive flights expose military aircraft to ground icing weather conditions for much longer periods of time than commercial aircraft, allowing the buildup of excessive ice and snow contamination on aircraft surfaces.
  • extensive pre-flight checks on sophisticated aircraft subsystems may require aircraft to remain on the ground, exposed to icing conditions for relatively long periods of time after being deiced (Arthur, D., Comments from a presentation on operational requirements for deicing/ anti-icing fluids, 317 AS Charleston AFB Reserves, Air Force Deicing Technology Crossfeed, Washington, DC, August, 1996).
  • the capability to rapidly remove and prevent the reformation of ice is essential to the readiness and safety of military air operations.
  • ice removal (deicing) of commercial and military aircraft have been accomplished by applying heated solutions of water and ethylene glycol (EG) or propylene glycol (PG) freezing point depressants (FPD).
  • EG ethylene glycol
  • PG propylene glycol
  • FPD freezing point depressants
  • These fluids are characterized by their ability to prevent ice formation on the aircraft surface for extended periods of time while the aircraft is awaiting takeoff during episodes of freezing or frozen precipitation. This extended period of ice protection, known as “holdover time”, is often obtained by adding thickeners or surfactants to the fluid. About 50 gallons of anti-icing fluid are used per aircraft.
  • Ethylene glycol is a listed hazardous air pollutant (HAP) and a listed groundwater pollutant in several states because of its toxicity and faces regulatory burdens in use, handling, and transportation (Oswalt, B.E., et al., "Use of Hazardous Materials for Aircraft Deicing," Report No. LM 930081, Air Force Logistics Management Agency, May, 1993).
  • Propylene glycol is an FDA approved food additive and has been shown to be virtually non-toxic to humans and terrestrial life.
  • Glycol-based freezing point depressants PEG and PG have relatively low aquatic toxicity.
  • BOD biochemical oxygen demand
  • Substances with a high BOD may deplete the dissolved oxygen in a receiving body of water such that the remaining dissolved oxygen is insufficient to support aquatic life.
  • Typical environmental regulatory guidelines call for a minimum dissolved oxygen content in receiving waters of 5 mg/L.
  • the five-day biochemical oxygen demand (BOD) for glycol-based freezing point depressants and commercially available deicing and anti-icing fluids range from about 400 to 800 g/kg, much greater than those found in typical raw municipal sewage (DTtri, F.M., "Deicers in Airport Stormwater Runoff," in Chemical Deicers and the Environment, p. 327, Lewis Publishers, 1991).
  • Fluids containing glycol freezing point depressants have typically been used to remove ice or prevent ice from forming on aircraft prior to takeoff.
  • Commercially available deicing fluids (SAE Type I) largely consist of combinations of ethylene glycol, diethylene glycol or propylene glycol freezing point depressants with water. These fluids may also contain surfactants, corrosion inhibitors, dyes, pH buffers, and chelating agents to produce required properties.
  • Commercially available anti-icing fluids SAE Types IIIII, and IV contain similar ingredients plus a thickener or a combination of surfactants to impart non-Newtonian rheological properties.
  • deicing and/ or anti- icing compositions that are biodegradable and non-toxic to animals and the environment. It would also be useful to be able to control or tailor the biodegradation rate, or short term (five-day) and ultimate BOD, of these compositions, depending on the environmental and hydrogeological conditions that prevail in a given body of receiving water. For example, if an airport's deicing fluid runoff enters a small, slow-moving body of water with limited ability to replenish dissolved oxygen from the atmosphere, a rapidly degrading substance with a high short term (5-day) BOD will deplete dissolved oxygen levels more than a slowly degrading substance with a lower short term (5-day) BOD.
  • This invention pertains to the development of environmentally- advantaged ice control materials which meet or exceed current performance requirements, are non-toxic to workers, and are inherently less damaging to the environment. Some of these formulations can be safely released to the environment without required runoff capture or post-treatment to achieve permit compliance. Other formulations can be captured and treated more efficiently and at lower cost than currently available fluids.
  • the invention also relates to the development of efficient, high performance ice control materials which reduce the amount of fluid needed to effectively protect aircraft from ice formation.
  • ice control material refers to deicers and anti-icers. Anti-icing fluids offer additional source reduction benefits because less material is wasted on runoff and overspray and repeat applications of fluids are avoided.
  • the invention relates to deicing compositions that have a tailorable BOD or rate of biodegradation.
  • the deicing compositions of the present invention comprise a) at least one first freezing point depressant (FPD) that is non-toxic, biodegradable and has a certain, i.
  • FPD first freezing point depressant
  • the present invention also relates to anti-icing compositions that have a tailorable BOD.
  • compositions comprise a) at least one first freezing point depressant (FPD) that is non-toxic, biodegradable and has a certain, i. e., predetermined, rate of degradation; b) at least one second FPD that is non-toxic, biodegradable, wherein the second FPD has a rate of degradation that is different from the rate of degradation of the first FPD; c) at least one surfactant, wherein the surfactant is non-ionic, non-toxic and biodegradable; and d) at least one thickener that is non-toxic and biodegradable; wherein the first FPD of (a) and the second FPD of (b) are present in a ratio that provides a composition that has a predetermined biochemical oxygen demand (BOD) .
  • FPD freezing point depressant
  • BOD biochemical oxygen demand
  • One embodiment of the present invention which is a slow degrading deicing fluid formulation contains a slow degrading freezing point depressant, e.g., triethylene glycol, and optionally, a rapidly degrading freezing point depressant, e.g., glycerol.
  • This formulation also contains a biodegradable, non-ionic surfactant, with low aquatic toxicity, e.g., ethoxylated sorbitan esters, polyoxyethylene esters, alcohol ethoxylates, alkyl polyglycosides.
  • Such a formulation would contain the slow degrading FPD at about 50-99.9%, the rapidly degrading freezing point depressant at about 0-50%, and the surfactant at about 0.1-1.0%.
  • a rapidly degrading, i.e., "biotreatable" deicing fluid contains: a rapidly degrading freezing point depressant, e.g., glycerol and a biodegradable, non-ionic surfactant, with low aquatic toxicity, e.g., ethoxylated sorbitan esters or polyoxyethylene esters.
  • a rapidly degrading freezing point depressant e.g., glycerol
  • a biodegradable, non-ionic surfactant with low aquatic toxicity
  • water is added to reduce viscosity and enhance blending and flow characteristics of deicer fluid.
  • the FPD is present at about 75-99.9% and the surfactant is about 0.1-1.0%. Water may be used up to about 25%.
  • the present invention provides for anti-icing fluids with tailorable rates of degradation.
  • an anti-icing compositions with a low short term (5-day) BOD to reduce the dissolved oxygen impact on receiving waters.
  • This type of fluid comprises a slow degrading FPD, e.g., triethylene glycol, as its primary freezing point depressant. It may further contain a rapidly degrading FPD, such as glycerol or another, e.g., propylene glycol, to tailor the degradation rate to meet specific requirements for a given airport runoff scenario.
  • This formulation also contains a non-toxic, biodegradable, thermally stable, non- Newtonian, polysaccharide thickener, e.g., welan gum, and a biodegradable, non-ionic surfactant, with low aquatic toxicity, e., g., ethoxylated sorbitan esters, polyoxyethylene esters, alcohol ethoxylates, alkyl polyglycosides.
  • a non-toxic, biodegradable, thermally stable, non- Newtonian, polysaccharide thickener e.g., welan gum
  • a biodegradable, non-ionic surfactant with low aquatic toxicity, e., g., ethoxylated sorbitan esters, polyoxyethylene esters, alcohol ethoxylates, alkyl polyglycosides.
  • an anti-icing formulation preferably contains 30- 70% of a slow degrading freezing point depressant, e.g., triethylene glycol, and optionally, up to about 50% of a rapidly degrading freezing point depressant, e.g., glycerol.
  • This formulation also contains from about 0.1- 1.0% of a polysaccharide thickener such as welan gum and from about 0.1- 1.0% of a non-ionic surfactant. The balance is water.
  • the present invention also provides for anti-icing compositions with enhanced biotreatability.
  • Such formulations utilize a freezing point depressant, e.g., glycerol, that is 100% biodegradable and has lower ultimate BOD than propylene glycol based fluids but approximately the same 5 day (short term) BOD.
  • the formulation contains surfactant and thickener additives that are also 100% biodegradable
  • the fluid's rapid degradation rate and reduced BOD are useful to airports that capture and treat their deicing fluid runoff in a waste water treatment system, a lagoon, or some other form of biotreatment system.
  • An example of such an anti-icing formulation contains from about 30-70% of a rapidly degrading freezing point depressant, e.
  • g., glycerol from about 0. 1-1.0% of a non-toxic, biodegradable, thermally stable, non-Newtonian, polysaccharide thickener, e. g., welan gum, from about 0.1-1.0% of a biodegradable, non-ionic surfactant, with low aquatic toxicity, e. g., ethoxylated sorbitan esters, polyoxyethylene esters, alcohol ethoxylates, alkyl polyglycosides.
  • the balance is water.
  • An anti-icing fluid formulation that is 100% biodegradable (including additives) can also be made based on the above formulations.
  • Preferred deicing fluids of the present invention comprise a freezing point depressant selected from triethylene glycol, glycerol, or a mixture of the two, and a biodegradable, low toxicity surfactant in an amount from about 0.1- 1.0 % by weight of the composition.
  • Other optional additives comprise dyes, preferably water soluble, and corrosion inhibitors. See e.g., Sastri, V.S., "Corrosion Inhibitors: Principles and Applications", John Wiley and Sons, May, 1998; Flick, Ernest, “Corrosion Inhibitors: An Industrial Guide", Noyes Publications, July, 1993.
  • the FPDs of deicing and anti-icing fluid formulations must be miscible in water, have a flash point greater than 100°C, be non-corrosive, be non-damaging to aircraft coatings and canopy materials, and depress the freezing point of water to -32°C or lower.
  • the FPDs for a specific formulation are selected from among a group of compounds meeting all of these requirements by one of ordinary skill in the art based upon the low human toxicity of the FPD, the BOD for the FPD and the desired BOD of the resulting ice-control composition.
  • Examples of FPDs comprise triethylene glycol, glycerol, propylene glycol, 1,3 butanediol, and tetraethylene glycol.
  • a slow degrading freezing point depressant is triethylene glycol
  • one example of a rapidly degrading freezing point depressant is glycerol.
  • the degradation rate of the ice control compositions and of the individual components of the compositions can readily be determined by one of ordinary skill in the art in accordance with the teachings herein and by methods known in the art. For example, as described further below, BOD and biodegradation rates can be input to computer models to estimate dissolved oxygen depletion in receiving waters.
  • Preferred anti-icing fluids of the present invention comprise (1) a freezing point depressant selected from triethylene glycol, glycerol, or a mixtures of the two, (2) a biodegradable, low toxicity surfactant, and (3) a thickener.
  • Preferred thickeners comprise a non-Newtonian, low toxicity, biodegradable, thermally stable thickener. Examples of preferred thickeners include polysaccharides or combinations of polysaccharides and clays. In preferred embodiments, the clay is hydrophobically modified clay.
  • water is added and optionally, other additives such as dyes, preferably water soluble, and corrosion inhibitors.
  • the components are present in the following amounts: 30-70% FPD, 30-70% water, 0.01-1.0% biodegradable, low toxicity surfactant, 0.1-1.0% non- Newtonian, low toxicity, biodegradable, thermally stable, polysaccharide thickener.
  • thickeners include welan gum, thermally stable xanthan gum, and combinations of a hydrophobically modified clay and a pdysaccharide, e.g., welan or thermally stable xanthan.
  • a preferred thickener comprises welan gum.
  • the surfactant for use in the present ice control formulations comprises a biodegradable, non-ionic surfactant, having low aquatic toxicity.
  • Surfactants in the previously described deicer and anti-icer formulations can be selected such that the formulation possesses very low aquatic toxicity (48 hour daphnia magna LC50>10,000 ppm). Examples include, e.g., ethoxylated sorbitan esters, polyoxyethylene esters, alcohol ethoxylates, and alkyl polyglucosides.
  • the 5-day BOD is in the range of about 40 g/kg to 840 g/kg.
  • ultimate BOD is less than approximately 1680 g/kg and 5-day BOD > approximately 90% of ultimate BOD.
  • Preferred anti-icing fluid compositions of the present invention have a Wet Spray Endurance Test (WSET) holdover time of greater than about 20 minutes.
  • Preferred deicing fluid compositions of the present invention when diluted with water to a ratio of 50:50, have a Wet Spray Endurance Test (WSET) holdover time of greater than about 3 minutes.
  • Other compositions of the present invention further comprise a corrosion inhibitor. Examples of corrosion inhibitors are known by the one of ordinary skill in the art.
  • the invention also relates to a method of selecting the biodegradation rate and 5-day BOD of a de-icing and anti-icing composition.
  • Preferred methods comprise: a) providing at least one first freezing point depressant (FPD) that is non-toxic, biodegradable and has a certain rate of degradation; b) providing at least one second FPD that is non-toxic, biodegradable and has a rate of degradation that is different from the rate of degradation of the first FPD; and c) providing at least one surfactant, wherein the surfactant is non-ionic, non-toxic and biodegradable; wherein the first FPD of (a) and the second FPD of (b) are present in a ratio that provides a composition that has a predetermined biochemical oxygen demand (BOD) .
  • FPD freezing point depressant
  • BOD biochemical oxygen demand
  • the present invention provides for ice control fluids with tailorable degradation rates which can be supplied as a concentrate for dilution with water by the user to obtain the desired mixture freezing point.
  • the invention further relates to a process for anti-icing or deicing an exterior surface of an aircraft, comprising applying to the exterior of the aircraft a deicing composition comprising: a) at least one first freezing point depressant (FPD) that is non-toxic, biodegradable and has a certain rate of degradation; b) at least one second FPD that is non-toxic, biodegradable, wherein the second FPD has a rate of degradation that is different from the rate of degradation of the first FPD; and c) at least one surfactant, wherein the surfactant is non-ionic, non-toxic and biodegradable; wherein the first FPD of (a) and the second FPD of (b) are present in a ratio that provides a composition that has a predetermined biochemical oxygen demand (BOD) .
  • BOD biochemical oxygen demand
  • Figure 1 shows the biodegradation rate of glycerol, triethylene glycol and a 50:50 mixture of glycerol and triethylene glycol.
  • Figure 2 shows receiving water #1 (small, slow moving stream), time
  • Figure 4 shows rheological behavior of FMI-5 compared with an industry leading Type IV anti-icer.
  • Figure 5 shows rheological data for formulation FM-1, 0.33 weight percent xanthan gum/50:50 ethylene dioxyethanol: water (ethylene dioxyethanol is commonly known as triethylene glycol)
  • Figure 6 shows rheological data for formulation FM-2, 0.33 weight percent xanthan gum/50:50 glycerol :water.
  • Figure 7 shows rheological data for formulation FM-3, 0.33 weight percent clay (MHEC)/50:50 glycero water.
  • Figure 8 shows rheological data for formulation FM-3, 1 weight percent clay (MHEC)/50:50 glyceroLwater.
  • Figure 9 shows rheological data for formulation FM-4, 0.33 weight percent welan gum /50:50 ethylene dioxyethano water.
  • Figure 10 shows rheological data for formulation FM-5, 0.33 weight percent welan gum/ 50: 50 glyceroLwater.
  • Figure 11 shows rheological data for formulation FM-6, 1 weight percent clay-xanthan gum/50:50 ethylene dioxyethanoLwater.
  • Figure 12 shows rheological data for formulation FM-7, 1 weight percent clay-xanthan gum/ 50: 50 glyceroLwater.
  • Figure 13 shows rheological data for formulation FM-8, 0.33 weight percent clay (MHEC)/50:50 ethylene dioxyethanoLwater.
  • Figure 14 shows rheological data for formulation FM-8, 1 weight percent clay (MHEC)/50:50 ethylene dioxyethanol: water.
  • Figure 15 shows a comparison of the rheological data for formulations
  • Figure 16 shows the rheological behavior (viscosity versus shear rate, on a logrithmic scale) of a 1% clay/ thermally stable xanthan mixture in a 1: 1 solution (by weight) of triethylene glycol and water compared with OCTAGON Type IV and UCAR Type IV.
  • Figure 17 shows the rheological behavior of a 1% clay/ thermally stable xanthan mixture in a 1: 1 solution (by weight) of glycerol and water compared with OCTAGON Type IV and UCAR Type IV.
  • Figure 18 shows the rheological behavior of a 1% clay/ xanthan mixture in a 1: 1 solution (by weight) of triethylene glycol and water compared with OCTAGON Type IV and UCAR Type IV.
  • Deicing fluids are applied to aircraft upon which frozen deposits (ice, frost, and snow) have already formed. The fluids are heated prior to application to aid in melting the frozen deposits for ease of removal. Deicing fluids normally have Newtonian viscosity profiles (i.e. their viscosity is independent of the rate of shear application) and do not have substantial holdover time. "Holdover time” is defined as the amount of time between the application of an ice control fluid and the time that frozen contamination first re-appears on the aircraft surface.
  • WSET Wet Spray Endurance Test
  • Anti-icing fluids are defined as ice control fluids with extended holdover time. Holdover times range from a minimum of 20 minutes in the WSET for Type II fluids to a minimum of 80 minutes in the WSET for Type IV fluids.
  • Many commercially available fluids contain a synthetic polymeric thickener additive that imparts non-Newtonian rheological properties to the fluid. The non-Newtonian properties of the fluid allow it to remain adhered to the aircraft surfaces, including sloped or vertical surfaces, while the aircraft is at rest (i.e. the fluid is in a zero or low shear condition) .
  • the present invention provides ice control formulations, which have a predetermined rate of degradation.
  • predetermined refers to a "controlled” or “tailored” rate of degradation and is accomplished by altering the selection and amounts of the freezing point depressants.
  • the FPDs are selected to produce various biodegradation rates, and thus, various short term (5 day) BODs. This is done, for example, by mixing a FPD with a slow rate of degradation with varying amounts of FPD with a rapid rate of degradation.
  • triethylene glycol which degrades slowly and has a low 5-day BOD
  • glycerol which degrades rapidly and has a higher 5 day BOD.
  • the degradation rates of triethylene glycol, glycerol, and a 50/50 mixture of triethylene glycol and glycerol are shown in Figure 1.
  • Aircraft ice control fluids must meet a rigorous set of performance and materials compatibility requirements, set forth by AMS 1424 (deicing fluids) and AMS 1428 (anti- icing fluids).
  • AMS 1424 deicing fluids
  • AMS 1428 anti- icing fluids
  • Aircraft SAE Type I "Deicing/ Anti-icing Fluid, Aircraft SAE Type I”
  • Aerospace Material Specification 1428 "Fluid, Aircraft Deicing/ Anti-icing Non-Newtonian (pseudoplastic), SAE Types II, III 86 IV”
  • the contents of these specifications are incorporated in their entirety.
  • Ice control formulations for use on aircraft must have the following characteristics: low freezing point; high flash point; low corrosivity; non-damaging to plastics and coatings; shelf stable and thermally stable.
  • anti-icers must be capable of preventing ice formation on aircraft surfaces for extended periods of time and be capable of shedding from the aircraft wings on takeoff.
  • the compositions of the present invention meet these criteria.
  • the ice control fluids of the present invention have a freezing point that is 10°C below the outside air temperature at which it is applied.
  • AMS 1428 requires a maximum freezing point of -32° C for anti- icing fluids.
  • Deicing fluids can be mixed -by the user with water in proportions which supply a suitable freezing point for the conditions of usage. In general, it is desirable for a deicing fluid to be capable of producing an aqueous solution with a freezing point of about -40°C, as this will be suitable under nearly all naturally occurring environmental conditions.
  • the de-icers and anti-icers of the present invention have a high flash point.
  • the flash point of deicing and anti-icing fluids must be greater than 100°C to avoid creating fire hazards when the fluid is heated. This requirement effectively eliminates the use of highly volatile freezing point depressants (those with flash points less than 100°C).
  • the anti-icing and deicing fluids of the present invention are not corrosive to metals commonly found on aircraft, including aluminum alloys, magnesium alloys, titanium alloys, and various types of steel. The fluids do not induce stress corrosion cracking in titanium or hydrogen embrittlement in high strength steels. Table 1 shows the results of corrosion tests performed on various formulation ingredients and mixtures.
  • the fluids do not contain alkali metals such as potassium or sodium, which promote high temperature conosion of metal alloys commonly found in aircraft engines.
  • the anti-icing and deicing fluids of the present invention are also non- damaging to plastics and coatings.
  • Aircraft deicing and anti-icing fluids must not damage typical non-metallic components of aircraft, including aircraft canopy materials and aircraft coatings. This requirement effectively eliminates organic materials with strong solvent characteristics towards polyurethane or a tendency to craze polycarbonate or acrylic materials.
  • compositions of the present invention are non-damaging to aircraft coatings and canopy materials.
  • Table 2 shows the results of plastic crazing tests and tests of effects on aircraft coatings using the ingredients and mixtures of formulations of the present invention. Tests were performed in accordance with conditions in AMS 1424 and AMS 1428. These results indicate that all ingredients and mixtures tested meet the requirements of AMS 1424 and AMS 1428 except pure (undiluted) triethylene glycol. Undiluted triethylene glycol (similar to propylene glycol, a freezing point depressant used in commercially available deicing and anti-icing fluids) causes slight crazing of acrylic plastic, a material used in some aircraft canopies. This indicates that deicing fluid compositions which consist of a concentrate of triethylene glycol (without added water) should not be allowed to be applied to an aircraft as a concentrate.
  • Prefened anti-icing and deicing fluids of the present invention have a stable shelf life and are thermally stable.
  • Deicing and anti-icing fluids are purchased, stored, and used in bulk over the course of one or more deicing seasons. Thus, their properties must remain stable over periods of time of up to one year.
  • Anti-icers must also be able to retain their rheological properties after exposure to elevated temperatures for long durations ( 70° C for 30 days). That is, they are thermally stable.
  • Anti-icers must be capable of preventing ice formation on aircraft surfaces for extended periods of time. This period of time, known as holdover time, is at least about 20 minutes, according to the standard WSET test for fluids designated as Type II and more than about 80 minutes according to the standard WSET test for fluids designated as Type IV.
  • the requirement for extended holdover time implies that an anti-icing fluid must effectively wet out and completely coat an aircraft's surface upon spray application. It also implies that the fluid must form a barrier film of sufficient thickness to prevent freezing precipitation from penetrating to the aircraft surface under low shear conditions.
  • the anti-icers must shed from the aircraft wings on take-off.
  • the anti-icing fluids possess a non- Newtonian (shear-thinning) viscosity profile with sufficiently low high shear viscosity.
  • the anti-icing compositions of the present invention meet these criteria.
  • deicing and anti-icing fluids which, although not cunently required by AMS 1428 or AMS 1424, are deemed necessary in order to produce a safe, effective, commercially viable deicing or anti-icing fluid.
  • One such notable characteristic is low conductivity. Fluids which are ionic in nature have a much higher electrical conductivity than fluids that are non-ionic. For example, potassium acetate runway deicers have very high electrical conductivities compared to runway deicing fluids based on glycols (ethylene or propylene) which do not contain organic salts. Applying fluids with high electrical conductivity presents a risk to aircraft electrical systems. If a conductive fluid contacts an improperly insulated electrical circuit, short circuiting will result. The compounds of the present invention have low conductivity.
  • the present invention provides for deicing and anti-icing compositions that are environmentally advantaged.
  • the term "environmentally advantaged” as used herein refers to compounds that: have low toxicity to humans and tenestrial animals and plants; have low toxicity to aquatic organisms and plants (LC50 preferably less than 10,000 ppm in a 48 hour acute daphnia magna test); are non-persistent and non-bioaccumulating (degrades in the environment and does not tend to accumulate in the tissues of organisms) and have a low risk of secondary toxicity effects through depletion of dissolved oxygen.
  • a biotreatable fluid is a 100% degradable fluid which degrades rapidly and contains no ingredients with high toxicity to microorganisms, and a reduced ultimate BOD (lower than commercially available fluids). This is applicable to users who capture and treat their runoff.
  • a "Low Dissolved Oxygen Impact Fluid” is a fluid containing a slowly degrading FPD that reduces the rate of removal of dissolved oxygen from receiving waters. This is applicable to users who release their fluid directly into receiving waters without treatment.
  • the present invention allows one of ordinary skill in the art to control the BOD of the ice control formulation to manufacture either a biotreatable fluid or a low dissolved oxygen impact fluid, depending on which type of fluid is desired.
  • Prefened formulations of the present invention have a rate of degradation such they comply with the requirements of the regulatory agencies, e.g., the EPA, for dissolved oxygen in the receiving waters.
  • the formulations result in a dissolved oxygen rate that does not fall below about 5 mg/liter.
  • the deicing fluids of the present invention comprise the following components: freezing point depressant (FPD); surfactants; and optionally, corrosion inhibitors, dyes and buffers.
  • FPD freezing point depressant
  • surfactants surfactants
  • corrosion inhibitors corrosion inhibitors
  • dyes dyes and buffers.
  • a freezing point depressant is used in the formulations to melt any incoming precipitation and to prevent the fluid itself from freezing as the fluid cools to ambient temperature. This ingredient has the highest concentration in the fluid; combined with water, it makes up over about 98% of the fluid.
  • LC50 refers to Lethal Concentration, 50%, which is the concentration of a substance at which 50% of the population of test organisms die. Ethylene glycol has also been listed by the EPA as a hazardous air pollutant (HAP).
  • FPDs that are useful in the present invention, e.g., based on the LD50 of the FPD.
  • prefened FPDs include, but are not limited to, propylene glycol, glycerol, and triethylene glycol, which are far less toxic to mammals than EG.
  • High LD50 numbers indicate lower toxicity. (Table 3) Toxicity studies on humans also indicate similar differences in toxicity among the glycols and glycerol.
  • FPDs on aquatic life and environment.
  • Preferred FPDs for use in the present invention have low aquatic toxicity, e.g., all of the glycols and glycerol have very low aquatic toxicity. (see Table 4, FPD aquatic toxicity data).
  • prefened FPDs for use in this invention are highly biodegradable.
  • the glycols and glycerol FPDs are all fully biodegradable.
  • Preferred FPDs, e.g., TG, PG and glycerol are water soluble (as opposed to fat-soluble) , so they do not persist in the environment, bioaccumulate, i.e., build up in the tissues or organs of animals or plants, or build up in sediments or soils.
  • ice-control formulations typically have secondary toxicity effects.
  • FPDs e.g., propylene glycol, glycerol, and ethylene glycol
  • FPDs having a fast rate of degradation higher 5 day BOD.
  • BOD biochemical oxygen demand
  • BOD biochemical oxygen demand
  • the theoretical oxygen demand is the amount of oxygen that would be consumed from the environment by the chemical if it were fully degraded. This number is usually reported in units of g/g (grams of oxygen per gram of organic substance). It can be calculated using the following equation:
  • ThOD 16(2x+y-z)/(6x+y+4z)
  • the BOD of the substance measured over time eventually approaches the ThOD.
  • BOD measurements are generally made over a limited period of time.
  • a common measurement of BOD is the 5-day BOD. This is the amount of oxygen required to degrade the pollutant in water over a 5-day period. Since some chemicals do not fully degrade in 5 days, the 5-day BOD for these chemicals will be less than the ThOD.
  • Comparing the 5-day BOD and the 20-day BOD of a substance to its ThOD is one method known in the art for establishing a degradation rate of a substance of interest.
  • FPDs When it is desired to have a rapidly degrading ice control formulation, FPDs are selected that have a BOD that approaches the ThOD for that FPD (i.e. the 5-day BOD should be greater than about 90% of the ThOD).
  • a fluid formulation consisting entirely of fully biodegradable components (ultimate BOD > 98% of ThOD).
  • a rapidly degrading, fully biodegradable fluid is prefened for airports that capture and treat aircraft deicing and anti-icing process runoff in a biotreatment facility such as a wastewater treatment plant or a holding pond.
  • a numerical model was used in formulating the ice control compositions of the present invention to determine the impact of BOD loading on dissolved oxygen concentration under several scenarios.
  • the model solves two differential mass balance equations, one each for BOD and dissolved oxygen.
  • the equations consider loading, advection, BOD deoxygenation, reaeration, and longitudinal dispersion.
  • the duration of the FPD discharge can be varied within the model.
  • a one-day discharge of a mass of fluid representative of fluid usage at a medium sized airport during winter storm conditions was specified.
  • BOD biochemical oxygen demand of the fluid
  • C concentration of the fluid
  • the model receiving waters were based on actual conditions in bodies of water which receive deicing fluid runoff at two medium sized commercial airports in the United States (Milwaukee, Wisconsin and Portland, Oregon).
  • Receiving Water No. 1 was specified as a wide, deep, slow-moving stream with little assimilative capacity and long travel times between the point of discharge and the mouth of the stream.
  • Receiving Water No. 2 was specified as a narrow, shallow, fast-flowing stream with a travel time of under two days.
  • the model scenarios are outlined in Table 5.
  • FPD #1 is a rapidly degrading FPD with degradation rate similar to glycerol.
  • FPD #2 is a slowly degrading FPD with degradation rate similar to triethylene glycol.
  • PG represents the typical degradation rate of a propylene glycol based aircraft deicing fluid.
  • Figures 2 and 3 show the dissolved oxygen content in the receiving stream at a given point in time as a function of downstream distance from the fluid's point of entry into the stream. These figures show that dissolved oxygen reaches a minimum at some point in time, i.e., a "sag point", after discharge. During this period of time, the fluid will have traveled some distance downstream.
  • glycerol In contrast to triethylene glycol, glycerol has a degradation rate similar to the "fast degrader" shown on the graph. In fact, even though glycerol's ultimate BOD (and theoretical oxygen demand) is 27% lower than propylene glycol's ultimate BOD, the two compounds produce almost identical dissolved oxygen sag in receiving waters due to the fact that glycerol degrades more rapidly than propylene glycol, and thus exerts a larger percentage of its ultimate BOD earlier in the degradation cycle.
  • Some airports have built special centralized aircraft deicing facilities with dedicated systems to capture runoff from the deicing operations. These airports may biotreat this runoff, e.g., by storing it for a period of time in a lagoon or sending the runoff to a wastewater treatment facility. For these applications, an ice control formulation that degrades rapidly is desirable.
  • Rapid degradation reduces the treatment time for the wastewater, and thus reduces the retention time and size required for the capital-intensive treatment facilities.
  • a fluid which has a higher percentage of glycerol, PG, or EG is prefened.
  • the surfactant comprises a biodegradable, non-ionic surfactant, with low aquatic toxicity. Examples include, e.g., ethoxylated sorbitan esters, polyoxyethylene esters, alcohol ethoxylates, and alkyl polyglucosides.
  • the amount of surfactant used in can be readily determined.
  • the amount of surfactant needed to lower the surface tension of the solution is up to about 0.4 wt% surfactant.
  • surfactants by their very nature can have toxic effects on aquatic organisms. They can coat surfaces or membranes required for the organism's oxygen exchange with the environment. Thus, it is advantageous for surfactants to degrade rapidly in the environment once their useful purpose has been served.
  • Preferred surfactants for use in the present formulations have low aquatic toxicity (Table 4) and are biodegradable (see Figure 2). Preferably they are soluble or dispersible in water, so that they form homogenous solutions or mixtures with the FPD/water mixtures in the fluid. Also it is preferred that the surfactant reduces the surface tension of the fluid below 35 dynes/cm (see surface tension, Table 6).
  • Additives are optionally added to ice control substances to enhance performance or meet specific user requirements.
  • additives include, but are not limited to, conosion inhibitors, dyes and buffers.
  • Conosion inhibitors may be required to allow the fluid to meet stringent conosivity requirements.
  • the fluid must not be corrosive to aircraft metals, including aluminum, titanium, magnesium, and steel alloys.
  • Dyes are added to deicers and anti-icers in order to aid the user in determining the type of fluid being applied and to enhance the visibility of the fluid on the aircraft wing.
  • Some formulations have additives that are sensitive to the pH level of the fluid (i.e. they only work within certain pH ranges) or have additives that change the pH of the fluid to unacceptable levels.
  • additives are present in aircraft deicing and anti-icing fluids in small concentrations (representing less than 2% by weight of the total fluid). Thus, even if they are biodegradable, they do not contribute significantly to the BOD of the fluid. However, additives are a primary source of aquatic toxicity in cunent state-of-the-art deicing and anti-icing fluids. The aquatic toxicity of pure ethylene or propylene glycol is approximately one order of magnitude lower than the aquatic toxicity of a fully formulated deicing fluid containing ethylene or propylene glycol.
  • the aquatic toxicity of the conesponding ethylene or propylene glycol based anti-icer is about two orders of magnitude greater than the pure freezing point depressant.
  • AFIT Air Force Institute of Technology
  • TTZ tolytriazole
  • APE's Alkyl phenol ethoxylates
  • the anti-icing compositions of the present invention further comprise a non-Newtonian thickener.
  • a non-Newtonian thickener can be added to the fluid to increase its viscosity at rest. This allows the fluid to stick to vertical or inclined surfaces without running off. The fluid must remain on these surfaces until the aircraft takes off in order to provide protection against incoming frozen or freezing precipitation.
  • An effective anti-icing fluid contributes to source reduction. Releasing less material to the environment directly impacts both BOD and toxicity concerns, since concentrations of the material in the receiving water will be reduced.
  • the waste associated with runoff of deicing fluid accounts for 70 to 90 percent of the deicing fluid used on the aircraft.
  • One approach to minimizing the environmental impact of anti-icers is to develop an extended holdover time anti-icing fluid.
  • the performance of an extended holdover time anti-icing fluid is largely determined by the non- Newtonian thickening agent.
  • the ideal thickening agent will have very high viscosity at rest, and yet it will thin out to a low viscosity when it is sheared.
  • Major aircraft anti-icing fluid manufacturers have dedicated considerable technical resources to developing improved thickening agents for increased holdover time fluids.
  • the state-of-the-art SAE "Type IV" fluids on the market have holdover times in freezing drizzle on the order of one hour and in high humidity conditions on the order of days. Use of fluids with holdover times equivalent to or better than Type IV fluids offers substantial safety and source reduction benefits.
  • anti-icing fluids have aquatic toxicity values that are orders of magnitude higher than their deicing fluid counterparts. Thus, it is desirable to have anti-icing fluids that are environmentally friendly.
  • n 1
  • the equation reduces to the Newtonian model, where the viscosity is constant with respect to the shear rate. If n ⁇ 1, the fluid is considered to be shear thinning; if n> 1 the fluid is shear thickening.
  • the log shear stress is plotted as a function of the log shear rate.
  • n which is related to the slope of the line
  • n Fluids with a low flow behavior index, n, will have a steep negative slope on the log viscosity versus log shear rate curve. This indicates a large decrease in viscosity as a function of shear.
  • a high intercept (“K”) is also desirable for an anti-icing fluid. This number represents the low shear viscosity of the fluid. Fluids with high K values can withstand shearing forces due to gravity and light winds without flowing. Thus, these fluids will remain on the aircraft and provide protection against icing while the aircraft is at rest.
  • preferred thickeners for use in the anti-icers of the present invention have higher K values, i.e., from about 500 to about 25,000, and low behavior index, n, i.e., from about -0.40 to about 0.80. These values can readily be determined by one of ordinary skill in the art in accordance with the above equation.
  • the thickener's rheological properties play a primary role in determining the thickness of the fluid film formed by spraying the fluid on an aircraft wing, and the relative amount of fluid that remains present on an inclined surface over a period of time.
  • anti-icing fluids are applied to aircraft when atmospheric temperatures are below freezing (below 0°C).
  • Current state-of-the-art anti- icing fluids are designed to be used at operational temperatures as low as - 20°C.
  • the viscosity of a fluid increases as temperature decreases. If the anti-icing fluid's high shear viscosity (i.e. the viscosity of the fluid under a rate of shear equivalent to the wind shear experienced on the wings of an aircraft during takeoff ) is too high, the fluid will fail to flow off of the wings of the aircraft on takeoff, resulting in a loss of lift and a potentially hazardous situation.
  • a prefened thickener does not change its rheological behavior significantly over the usage temperature range of interest (from about 0°C to -20°C).
  • anti-icing fluids In addition to providing consistent low temperature rheological properties, anti-icing fluids must be able to withstand high temperature extremes without significant alteration of rheological properties. Anti-icing fluids can be exposed to elevated temperatures for long periods of time during storage over the summer months. The AMS 1428 specification therefore requires that anti-icing fluids retain 90% of their low shear viscosity value after exposure to elevated temperatures of 70°C for 30 days. In addition, anti-icing fluids may sometimes be applied after heating to temperatures approaching 100°C. This occurs when a user decides to apply the anti-icing fluid in a one-step process, in which deicing (removal of ice already formed on a surface) is accomplished simultaneously with anti-icing (prevention of future ice formation on a surface).
  • welan gum is a prefened thickener.
  • Welan gum provides excellent rheological characteristics and is unusually thermally stable. Thermal stability test using the methods described in the AMS 1428 specification, showed that welan gum met the anti-icer specification requirement (i.e., neither losing less than 20% of its viscosity nor gaining more than 10% after 30 days of exposure to 70 °C.)
  • the thickener includes combinations of polysaccharides and clays.
  • the clay is treated, e.g., hydrophobically modified.
  • Appropriate clays can readily be selected by one of ordinary skill in the art. Examples of useful clays include suspensions of small particles of clay, including types of clay classified as montmorillinite (also sometimes referred to as smectite clays, and include clays referred to as hectorite. bentonite, and montmorillinite), illite, and attapulgite.
  • the prefened clay is a montmorillinite clay.
  • the clay is purified montmorillonite clay (NANO No. 73, lot No. AN-237-97, from Nanocore, Inc.).
  • Examples of the polysaccharides that are combined with the clays include those described above, e.g., welan gum, xanthan gum, and other known in the art.
  • the present invention is further illustrated by the following Examples. The Examples are provided to aid in the understanding of the invention and are not construed as a limitation thereof.
  • deicing fluid compositions set forth in the following examples are made by thoroughly blending ingredients together at room temperature.
  • Anti-icing fluid compositions... Marina should supply a paragraph explaining how she dispersed the welan gum in the mixture since it is not completely straightforward .
  • EXAMPLE 1 Composition of slowly degrading (low 5-day BOD) deicing fluid.
  • EXAMPLE 4 Composition of deicing fluid with more rapid degradation (higher 5-day BOD) than Example 3.
  • EXAMPLE 5 Composition of deicing fluid with more rapid degradation (higher 5-day BOD) than Example 4. The following components are mixed together: Triethylene glycol 49.3 wt %
  • EXAMPLE 6 Composition of biotreatable deicing fluid.
  • EXAMPLE 7 Composition of biotreatable deicing fluid with improved flow and handling characteristics.
  • EXAMPLE 8 Composition of slowly degrading (low 5-day BOD) anti-icing fluid.
  • EXAMPLE 10 Composition of anti-icing fluid with more rapid degradation (higher 5-day BOD) than Example 9.
  • EXAMPLE 11 Composition of anti-icing fluid with more rapid degradation (higher 5-day BOD) than Example 10.
  • EXAMPLE 12 Composition of biotreatable anti-icing fluid.
  • EXAMPLE 13 Composition of anti-icing fluid thickened with welan gum and hydrophobically modified.
  • Triethylene glycol 43.2 wt % Glycerol 14.4 wt % Water 41.0 wt %
  • compositions can be prepared as a concentrate and then diluted by the user as needed for the particular use or method of application.
  • the resulting solution was mixed with a freezing point depressant (triethylene glycol or glycerol ) to yield a 50:50 composition (50 wt% water plus clay/MeHEC, 50 wt % FPD).
  • a freezing point depressant triethylene glycol or glycerol
  • the rheology of various concentrations of clay/MeHEC, mixtures of clay/MeHEC with xanthan gum, and MeHEC alone in the FPD/water solution were measured. Comparison was made to the commercially available Type IV fluids, both at ambient temperature and at 0°C. When clay/MeHEC was added at a concentration of about lwt% to freezing point depressant/ water solutions, its rheological properties were similar to those of a commercially available Type IV fluid. See Figures 16-18.
  • Table 9 lists some anti-icing formulations containing a freezing point depressant (glycerol or ethylene dioxyethanol, commonly known as triethylene glycol) and a thickening agent(s) (xanthan gum, welan gum, clay and clay treated with methyl-2-hydroxyethylcellulose (MeHEC)).
  • the FPDs have about a 27 to 50 percent lower 20 day, room temperature BOD than the glycols and have rheological characteristics comparable to commercially available anti-icing fluids.
  • the concentrations of the freezing point depressant (FPD) in water range from 20 to 80 percent, while the concentration of the thickening agent ranges from 0 to 3 percent.
  • Figures 5 through 14 show the rheological characteristics (viscosity vs shear rate) for each of the anti-icing formulations at room temperature (25°C) listed in Table 9 for illustrative values of the freezing point depressant concentration and thickening agent concentration.
  • cellulose-treated clay in a water/ ethylene dioxyethanol mixture showed rheological characteristics similar to UCAR Type IV anti-icing fluid, 0.5 percent xanthan gum, and 0.5 percent welan gum.
  • the viscosity of cellulose-treated clay in water/ glycerol mixture was lower. This parameter can be improved by changing the percentage of modified cellulose in the clay composition or by increasing the concentration of the clay. Since the temperature effects in an anti-icing fluid should be minimal, the temperature effect (expressed as a ratio of viscosity at corresponding temperatures) was studied. The cellulose-treated clay exhibited the lowest temperature-thinning effect in water/ ethylene dioxyethanol and in water/ glycerol mixtures.
  • the effect was similar to the one of UCAR and xanthan gum.
  • untreated 1 percent MeHEC in water/ ethylene dioxyethanol and in water/ glycerol mixture showed the highest temperature-thinning effect.
  • the highest shear- thinning effects were observed in xanthan gum and welan gum in water/ glycerol, but the shear-thinning effect in clay-cellulose mixture was similar to UCAR Type IV.
  • the flow index of the MeHEC-treated clays was comparable to the one of UCAR TYPE IV as well as xanthan gum.
  • the flow index of the untreated MeHEC was by far higher, indicating substantial improvement in the shear thinning.
  • EXAMPLE 14 The following anti-icing compositions were made:
  • FM-1A 0.22g of welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.2g Dl water .
  • surfactant Emerest 2660 PEG- 12- oleate (Cognis) was dissolved in the dispersion followed by mixing with 57.
  • FM-2A 0.22g of welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.2g Dl water .
  • FM-3A 0.33g welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.16 g Dl water . 0.2g of surfactant Emsorb 6900 (Cognis) was dissolved in the dispersion followed by mixing with 57. 31g of triethyleneglycol (Aldrich).
  • FM-4A 0.33g welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.16 g Dl water . 0.2g of surfactant Emerest 2660 (Cognis) was dissolved in the dispersion followed by mixing with 43. Og of triethyleneglycol (Aldrich) and 14.3 lg glycerol(Aldrich) .
  • FM-5A 0.22g of welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.12g Dl water .
  • surfactant Emsorb 6900 (Cognis) was dissolved in the dispersion followed by mixing with 57.27g of triethyleneglycol (Aldrich) .
  • FM-6A 0.22g of welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.12g Dl water . 0.4g of surfactant Emerest 2660 (Cognis) was dissolved in the dispersion followed by mixing with 42.96g of triethyleneglycol (Aldrich ) and 14.3 lg glycerol(Aldrich).
  • FM-7A 0.33g welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.07 g Dl water .
  • surfactant Emerest 2660 (Cognis) was dissolved in the dispersion followed by mixing with 57.2g of triethyleneglycol (Aldrich) .
  • FM-8A 0.33g welan gum (lot #913914K) obtained from Monsanto was dispersed in 42.07 g Dl water .
  • surfactant Emerest 2660 (Cognis) was dissolved in the dispersion followed by mixing with 42.9g of triethyleneglycol (Aldrich) and 14.3g glycerol(Aldrich).

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Abstract

L'invention concerne des formulations de contrôle de la glace (compositions dégivrantes et antigivrantes) présentant une DBO adaptable. Les compositions dégivrantes selon l'invention contiennent a) au moins un premier additif antigel non-toxique, biodégradable, et présentant une certaine vitesse de dégradation, b) au moins un deuxième additif antigel non-toxique, biodégradable, le deuxième additif antigel présentant une vitesse de dégradation différente de celle du premier additif antigel, et c) au moins un surfactant non-ionique, non-toxique, et biodégradable, le premier additif antigel selon a) et le deuxième antigel selon b) étant présents dans une proportion donnant une composition qui présente une demande biochimique d'oxygène (DBO) prédéterminée. L'invention concerne également des compositions antigivrantes contenant en outre un épaississant.
EP00973654A 1999-10-18 2000-10-18 Compositions degivrantes et antigivrantes ecologiques Withdrawn EP1238038A4 (fr)

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US6861009B1 (en) * 2003-03-06 2005-03-01 E. Greg Leist Deicing compositions and methods of use
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EP1240269A4 (fr) 2007-05-23
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CA2387923A1 (fr) 2001-04-26

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