CA1331084C - Aircraft de-icing and anti-icing composition - Google Patents
Aircraft de-icing and anti-icing compositionInfo
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- CA1331084C CA1331084C CA 517026 CA517026A CA1331084C CA 1331084 C CA1331084 C CA 1331084C CA 517026 CA517026 CA 517026 CA 517026 A CA517026 A CA 517026A CA 1331084 C CA1331084 C CA 1331084C
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Abstract
ABSTRACT
A composition is described which consists of a microemulsion of oil in a water/glycol solution and containing certain thickening agents, emulsifiers, carboxylic acids having from 10 to 18 carbon atoms and alkanolamines to provide the desirable viscosity and shear stability needed to give a composition having effective de-icer and anti-icing properties.
A composition is described which consists of a microemulsion of oil in a water/glycol solution and containing certain thickening agents, emulsifiers, carboxylic acids having from 10 to 18 carbon atoms and alkanolamines to provide the desirable viscosity and shear stability needed to give a composition having effective de-icer and anti-icing properties.
Description
AIRCRAFT DE-ICING AND ANTI-ICING COMPOSITION
This invention relates to a composition comprising a microemulsion of oil in a water/glycol solution which has both de-icing and anti-icing properties when applied to aircraft surfaces. More particularly, it relates to a composition which removes ice from aircraft wing surfaces yet has the desirable viscosity and shear stability to provide improved anti-icing on such surfaces.
The use of glycol/water solutions to remove snow and ice from aircraft surfaces has been known for many years. Aqueous solutions containing, for example, approximately equal parts of ethylene glycol and water are good de-icing agents because of its relatively low -freezing point. However, such a mixture offers ]ittle or no anti-icing properties under severe snow and ice conditions. -~
To increase the anti-icing performance of such de-icing agents thickeners have been added to the -solution to increase its adhesion to aircraft surfaces ~ - -thereby increasing its retention property. In the anti-icing agent described in U.S. Patent No. 4,358,389 crosslinked polyacrylates are used. When sprayed on `~
aircraft by means of conventional de-icing equipment the solution would suffer a severe loss of rheological - -~
., . ~ ~ ,.
.
properties, thereby compromising its performance as an anti-icing agent. In general, most commercially- - -available water soluble thickening agents when used in -- -the proper concentrations in the glycol/water solution -- -will provide the necessary retention time on the - :;
aircraft surface to function as an anti-icing agent.
However, high molecular weight thickeners, such as polysaccharides, polyacrylic acid, etc., which are capable of providing thixotropic properties to such a ~- ;
solution, are generally preferred. This is mainly due J'.. ''., ,' ,'' to the fact that they offer better flow-off ;
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.
.. ;.
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characteristics under dynamic or shear stress conditions on the aircraft surface.
Another thickener used in some de-icing compositions is xanthan gum, with up to 5%
concentrations of the gum being recommended. This thickener is said to provide ease of handling in concentrated solutions of the de-icer. Xanthan gum has one of the best shear stability characteristics of any known polymer. However, increasing the shear stability of a de-icer solution by the addition of xanthan gum in high concentrations alone is not the most desirable method of designing an aircraft de-icing and anti-icing fluid. At high concentrations, the xanthan gum is known to gel in the presence of buffers and corrosion inhibitors. In the field of enhanced oil recovery, for example, gelling of a xanthan gum solution can be induced easily by the use of certain metal ions for use as fracturing fluids. As gelling and polymer separation occur in aircraft de-icing fluids especially during storage, the loss of the bulk fluid viscosity may render -the de-icer ineffective as an anti-icing agent. Clearly there is a need to stabilize such a system from gelling. `
The present invention is directed towards the provision of a microemulsion of oil in a water/glycol solution for a synergistically thickened de-icing and anti-icing composition having improved storage stability, as well as desirable shear stability, thermal stability and rheological properties.
The present invention also is directed towards the provision of an aircraft de-icing and anti-icing composition having improved storage stability as well as a desirable shear stability, thermal stability and rheological properties.
In accordance with one aspect of the present invention, there is provided a de-icing and anti-icing composition, comprising a microemulsion having a continuous phase and a discontinuous phase, the continuous phase comprising:
(a) from 5% to 85% by weight based on the weight of the total composition of a glycol, and (b) from 5% to 95% by weight of water based on the weight of the total composition;
the discontinuous phase comprising:
from 0.01% to 5.0% by weight based on the total weight ~;
of the composition of a water insoluble oil, the oil comprising carboxylic acid having from 10 to 18 carbon atoms in an amount of an 0.1 to 2.5% by weight, based on the total weight of composition, and the remainder of the composition comprising:
(c) from 0.05% to 10.0% by weight based on the ~
weight of the total composition of a -thickening agent selected from the group consisting of natural and artificial gums, cellulose ethers, carboxymethylcellulose and ~ -~
hydroxyethylcellulose, and (d) an emulsifier selected from the group ~
consisting of anionic surfactants and `-non-ionic surfactants and mixtures thereof, - `~
said emulsifier being present in an amount of from 0.1 times to 100 times the concentration - ~-of the water insoluble oil, and - ~-(e) from 0.1% to 2.5% by weight of alkanolamines based on the weight of the total composition, - ~
the total composition having a pH of from 6 to - -The compositions of this invention are in the ~ ;
form of a microemulsion. The term "microemulsion" `~
connotes that the composition appears clear but the ;~
occluded phase (i.e., the non-continuous phase) is still able to effect the refraction of light. Generally, the - ;-occluded phase has droplet sizes less than 0.5 microns in diameter and in many instances the occluded phase :
i~1084 comprises micelles. Microemulsions are characterized by having the oil dispensed in mlcro-droplets in the aqueous solution so that these droplets are smaller than the wavelength of visible light and consequently the microemulsion appears transparent. Procedures for preparing microemulsions are fully described in the textbook "Microemulsion Theory and Practice", Leon M.
Prince, Editor (Academic Press, Inc. 1977).
Advantageous compositions of this invention provide excellent de-icing and anti-icing properties, shear stability, and rheological properties such that the compositions are readily removed from the aircraft surfaces during takeoff, even at temperatures below O.C, - -e.g., to -20.C. Moreover, the properties of the compositions are not unduly affected by evaporation of water after application to a surface. The compositions also exhibit good storage stability, particularly with the composition using xanthan gum thickening agents.
The compositions of the present invention are characterized by a continuous phase comprising water and glycols meaning that the water/glycols phase extends through all parts of the microemulsion in a continuous fashion. This combination can vary from a water concentration of from 25% to 95% by weight based on the total weight of the composition. The preferred water composition range for the de-icer and anti-icer composition is from 40% to 50% by weight of the total composition.
The glycols useful in the continuous phase composition include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and mixtures thereof.
The oil which forms the discontinuous phase of the composition includes, but is not limited to, non-polar and partially polar, alipbatic and aromatic oils, such as mineral oil, paraffin oil, silicone oil, ~ : : ' ~
.: ~ .
' - ~
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propylene oxide/ethylene oxide copolymers as well as sulfated, sulfonated, phosphated and phosphonated oils and the like. The oil comprises a carboxylic acid -; -having from 10 to 18 carbon atoms in the amount of from 0.1 to 2.5% by weight based on the total weight of composition. The amount of such oil present in the ;
microemulsion with the continuous phase components of the composition of this invention should be in the range - ~ -of from 0.01% to 5.0% by weight based on the total weight of the composition. The preferred range is 0.1%
to 1.0% by weight based on the total weight of the invention.
The water soluble thickening agent useful in :
the present invention to improve the anti-icing -characteristics of the composition includes starches, --modified starches and starch derivatives, as well as -natural and artificial gums, cellulose ether, ~ -carboxymethylcellulose, hydroxyethylcellulose, ; - -~
methylcellulose and their derivatives, ethylene oxide/
proplyene oxide copolymers, polyvinyl alcohol and their - ;;
related products. The amount of such thickening agent ~ - -can vary from 0.05% to 10.0% by weight based on the ~ ~-total weight of the composition. The preferred ranged is from 0.05% to 5% by weight based on the total weight of the composition. ; ;~
The emulsifiers used in the present composition can include any of a wide range of anionic surfactants, such as organo-phosphates, phonphonates, ~-sulfates and sulfonates, as well as fatty acid salts and non-ionic surfactants, such as alcohols, phenols, ;
amines, fatty acids and their alkoxylated derivatives and the like. The above anionic and non-ionic surfactants can be used singly or preferably in a combination of at least two surfactants, to facilitate microemulsification. The amount of emulsifier required to produce the desired microemulsion is from 0.1 times ~A : -:
,. .
.
- 1331~
to about loo times the concentration by weight of the oil present in the composition. The preferred range is from about 2 times to 20 times the concentration by weight of the oil.
The composition of the present invention is blended into a microemulsion in order that the de-icing and anti-icing composition will maintain storage stability, clarity and flow characteristics even when stored under the freezing temperatures that prevail in aircrat hangers in northern climates during the winter months.
The de-icing and anti-icing composition of this invention should have a pH of between 6 and 10 with a preferred range between 7 and 9. Buffers can be included in the composition to provide this pH range.
Suitable buffers include, but are not limited to, borates, phosphates, carbonates, benzoates or mixtures thereof. Such buffer, if used, preferably is employed in an amount of between 0.1% to 2.0% by weight of the total composition.
One minor additive that is particularly desirable is a defoamer in view of the substantial ~
quantities of emulsifier employed in the composition. -Any commercially available defoamer or anti-foamer can -be used, but a particularly preferred defoamer is a silicone defoamer of Union Carbide sold under the trade , mark SAG. The amount of this defoamer to be used is preferably in the range of from 0.05% to 0.5% by weight -based on the weight of the total composition. -~
The anti-icing property of the invention can be measured by the use of the following procedure. A
mixture of ethylene glycol and water at a ratio of 88:12 -~ -is used as a reference material because of its known - ;~
anti-icing property. Under the set condition of -8~C
and at a precipitation rate of 1.08 mm/hr, the : '.
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, . ,, .- .
reference material was measured to have 15 minutes of ~ -anti-icing time.
As an illustration, both the reference material and a composition of the present invention were applied to the surfaces of two separate aluminum panels cooled to -20C. A mist of freezing water then was - ~
sprayed onto the surfaces until frostication occurred in --both cases. The times elapsed were recorded. Based on the 15 minute anti-icing protection time of the reference material, the protection time of the invention composition could be calculated.
While the anti-icing time of any composition varied as a function of the temperature and ;~
precipitation rates, it was estimated that a de-icing, anti-icing fluid of a yield value of 1 dyne/cm2 would -give approximately 2 hours of anti-icing protection ~; ;;
under the temperature and precipitation conditions as -mentioned above. The yield value is defined as the minimum amount of force required to initiate the flow of a fluid from its rest state. In general practice, it can be approximated by the use of Brookfield LVT
viscosities. -~
The following Examples of de-icing and anti-icing compositions of the present invention are set forth for purposes of illustration, but are in no way intended to limit the scope of the invention.
:;,, ', ExamDle 1 ~ , A microemulsion composition of the invention -was prepared by mixing ethylene glycol, water and mineral oil vigorously at up to 70C, together with the other components, to form the de-icer and anti-icing composition. The microemulsion was allowed to cool slowly to room temperature (25C). The resulting product had a clear bright appearance and contained the following components in percentages by weight based on '.
:, ., .
, the total weight of the composition:
(a) 84.0% ethylene glycol (b) 2.0% dipotassium hydrogen phosphate~
(c) 0.1% xanthan gum (d) 6.9% water ~ (e) 1.0% white mineral oil 10 cst ^~ (f) 1.5% carboxylic acid having from 10-18 carbonatoms -.
(g) 1.5% triethanolamine (h) 3.0% of a mixture of non-ionic surfactants of Example 2 A ~icroemulsion was prepared to demonstrate the synergistics of the following components, the percentages given are percents by weight based on the : r total weight of the composition:
(a) 40.0% ethylene glycol (b) 14.0% diet ffl lene glycol (c) 41.7% water (d) 2.0% dipotassiu~ hydrogen phosphate :
(e) 0.1% xanthan gum (f) 0.25% mineral oil (g) 1.0% carboxylic acid having from 10-18 carbon -~
. 25 atoms ~ (h) 0.7% triethanolamine :~ (i) 0.25% of a mixture of non-ionic surfactants of H~3 5-14 .-~-The yield value of the de-icing and anti-icing agent at -S-C in the absence of components - (f) through (j) was found to be 0.14 dyne/cm2 while a compo~ition containing all of the ~bove compononts gives a yield value of 1.0 dyno/cm2 under the ~ame tomperature conditions. This corr-~ponds to a significant `~
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133108~
improvement in rheological properties due to the synergistic activity between the xanthan gum and the microemulsion. The yield value is defined as the minimum amount of force required to initiate the flow of a fluid from its rest state. In general practice, it can be approximated by the use of Brookfield LVT
viscosities . , Example 3 lo A de-icing and anti-icing composition containing silicone oil was prepared by mixing the following components in a microemulsion. Again, the amounts are in percent by weight based on the total weight of the composition: - -(a) 40.0% ethylene glycol (b) 14.0% diethylene glycol (c) 41.4% water (d) 0.1% xanthan gum (e) 0.2% tolyltriazole - -(f) 1.0% carboxylic acid having from 10 to 18 carbon atoms (g) 1.0% triethanolamine (h) 1.0% of a mixture of non-ionic surfactants of (i) 0.3% potassium hydroxide (j) 1.0% dimethyl polysiloxane (10-20 cSt) This composition had substantially the same yield value as in Example 2.
Example 4 A de-icing and anti-icing composition similar ~
to the sample prepared in Example 3 can be obtained by ~ ~ :
replacing the dimethyl polysiloxane with 0.25% by weight of propylene oxide based synthetic oil of 300 SUS ;
viscosity to give the same magnitude of synergistic thickening activity as in Example 2.
,. -1 33108~
Example 5 Another composition containinq anionic surfactants was prepared by mixing the following components in a microemulsion: ~
(a) 36.0% ethylene glycol -:
(b) 18.0% diethylene glycol :
(c) 42.27% water (d) 0.3% potassium hydroxide :~
(e) 0.2% tolyltriazole ~ :
(f) 0.13% xanthan gum -:
(g) 1.0% carboxylic acid having from 10 to 18 carbon atoms :
(h) 1.0% triethanolamine (i) 0.5% sodium arylalkylsulfonate :.
(j) 0.5% phosphorester 600 anionic surfactant (k) 0.1% mineral oil The yield value calculated based on the Brookfield viscosities at -5 C is 1.26 dyne/cm2.
Example 6 A de-icer and anti-icing composition having a : relatively high yield value of 17.0 dyne/cm2 was :~
prepared by use of the following components in percent by weight based on the total weight of the composition : ~ m-:~
to demonstrate the increase in shear stability of the ~` microemulsified fluid: .`~
(a) 36.0% ethylene glycol ~ ;s:~
(b) 18.0% diethylene glycol (c) 41.95% water :: ~ -(d) 0.3% potassium hydroxide ~ :
(e) 0.2% tolytriazole - (f) 0.3% xanthan gum .
(g) 1.0% carboxylic acid having 10-18 carbon atoms : 35 (h) 1.0% triethanolamine ~ ;
: ' . :,'.: "~:, ~
133108~
(i) 1.0% of a mixture of non-ionic surfactants of (j) 0.25% mineral oil . :
When sheared by the use of a Brookfield counter-rotating mixer for 5 minutes at 3500 rpm, the .
yield value reduced to 14.4 dyne/cm2 while the composition without microemulsion gives a yield value of :
only 12 dyne/cm2.
Exam~le 7 A similar composition to that described in Example 6 was prepared by microemulsifying the following ~ -components in percent by weight based on the total weight of the composition to demonstrate the synergistic thickening activity using a water soluble polymer other than xanthan gum:
(a) 40.0% ethylene glycol -(b) 14.0% diethylene glycol ~ ~
(c) 41.65% water - ~ :
(d) 0.3% potassium hydroxide ~ ~:
(e) 0.2% benzotriazole (f) 0.5% carboxy methyl cellulose : ;
(g) 1.0% carboxylic acid having 10-18 carbon atoms (h) 1.0% triethanolamine (i) 1.0% of a mixture of non-ionic surfactants of HLB 5-14 . .
(j) 0.35% mineral oil ~
,, The yield value of the composition in the ~ ~;
absence of components (g) through (j) at -18~C is zero.
While incorporating components (g) to (j) gives a value , .
of 0.40 dyne/cm2. The use of the microemulsion with the ~ :
mineral oil, carboxylic acid and other components has in . ~ -~
fact rendered thilotropic property to the polymer in the water/glycol solution. : :
,_, , . `' '5 '`'.` . " " ' " ~ '' ' " '~ ' ' " '' 1331n~a SUPPLEMENTARY DISCLOSURE
The principai specification describes de-icer and anti-icing compositions consisting of a microemulsion having a continuous phase and a discontinuous phase and comprising a variety of components. Certain~~pecific -~
~ Examples of suitable compositions are described.
~~ The following Table I sets forth additional compositions of this invention that have desirable de-icing and anti-icing properties and advantageous rheological properties with shear stability and storage stability: ~
TABLE I ~-(all percentages are by weight based on the total composition) - -Composition Composition Composition Com~ound A % B % C %
Monoethylene glycol 36 37 - -Diethylene glycol 18 18 Triethylene glycol - - 55 - ~ -Water 42.3 41.9 41.87 - ~ ---Xanthan Gum 0.13 0.1 0.1 -Ammonium polyacrylate 0.5 - -Isosteric Acid 1.0 1.0 1.0 ~
Triethanol Amine 1.0 1.0 1.0 ~ --Non-ionic surfactants, HLB 5-14 1.0 1.0 1.0 Potassium hydroxide (so%) 0.06 0.04 0-04 .. : ~ :. :-One component of the composition of the invention is a glycol. Mentioned in the principal disclosure as useful glycols are ethylene glycol, ! diethylene glycol, ~ropylene glycol, dipropylene glycol and mixtures thereof. Other useful glycols include triethylene glycol and glycerol, which may be employed in adm$xture with each other or with the glycols described in the principal disclosure. See, for D
instance, U.S. Patents nos. 2,373,727; 3,940,389 and 4,358,389.
Another essential component of the compositions of the invention as described i~ the 5~ principal disclosure is from 0.01 to 5.0% by ~eight of a ~ -_ water-insoluble oil, which is described in the principal disclosure as including a carboxylic acid having from 10 -to 18 carbon atoms. In accordance with this supplementary disclosure, the discontinuous phase may comprise up to 5.0% (preferably at least about 0.01%) by weight of the total composition of the water-insoluble -oil and such water-insoluble oil may comprise at least one substantially water-insoluble, partially polar ~ -compound in an amount of from 0.1 to 2.5% by weight based on the weight of the total composition.
Such polar compounds include carboxylic acids, sulfuric acids, phosphoric acids, salts and polar esters thereof having hydrocarboxyl substituents of at least about 6, often 10 to 40, eg. 10 to 18, carbon atoms per polar group. In addition to the carboxylic acids having from 10 to 18 carbon atoms described in the prin-cipal disclosure, preferred water-insoluble partially polar compounds include hydrocarboxyl-substituted polyacrylate in which the hydrocarboxyl substituents have from about 6 to 40 carbon atoms. Generally, the molecular weight of the hydrocarboxyl-substituted polyacrylates is less than about 100,000, say about 700 to 50,000.
The partially polar compounds will usually comprise a microemulsion of micelles. The addition of ;
further water insoluble oils generally leads to an increase in the micelle size.
This invention relates to a composition comprising a microemulsion of oil in a water/glycol solution which has both de-icing and anti-icing properties when applied to aircraft surfaces. More particularly, it relates to a composition which removes ice from aircraft wing surfaces yet has the desirable viscosity and shear stability to provide improved anti-icing on such surfaces.
The use of glycol/water solutions to remove snow and ice from aircraft surfaces has been known for many years. Aqueous solutions containing, for example, approximately equal parts of ethylene glycol and water are good de-icing agents because of its relatively low -freezing point. However, such a mixture offers ]ittle or no anti-icing properties under severe snow and ice conditions. -~
To increase the anti-icing performance of such de-icing agents thickeners have been added to the -solution to increase its adhesion to aircraft surfaces ~ - -thereby increasing its retention property. In the anti-icing agent described in U.S. Patent No. 4,358,389 crosslinked polyacrylates are used. When sprayed on `~
aircraft by means of conventional de-icing equipment the solution would suffer a severe loss of rheological - -~
., . ~ ~ ,.
.
properties, thereby compromising its performance as an anti-icing agent. In general, most commercially- - -available water soluble thickening agents when used in -- -the proper concentrations in the glycol/water solution -- -will provide the necessary retention time on the - :;
aircraft surface to function as an anti-icing agent.
However, high molecular weight thickeners, such as polysaccharides, polyacrylic acid, etc., which are capable of providing thixotropic properties to such a ~- ;
solution, are generally preferred. This is mainly due J'.. ''., ,' ,'' to the fact that they offer better flow-off ;
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.
.. ;.
: 2 ~ 3 ~' ~
characteristics under dynamic or shear stress conditions on the aircraft surface.
Another thickener used in some de-icing compositions is xanthan gum, with up to 5%
concentrations of the gum being recommended. This thickener is said to provide ease of handling in concentrated solutions of the de-icer. Xanthan gum has one of the best shear stability characteristics of any known polymer. However, increasing the shear stability of a de-icer solution by the addition of xanthan gum in high concentrations alone is not the most desirable method of designing an aircraft de-icing and anti-icing fluid. At high concentrations, the xanthan gum is known to gel in the presence of buffers and corrosion inhibitors. In the field of enhanced oil recovery, for example, gelling of a xanthan gum solution can be induced easily by the use of certain metal ions for use as fracturing fluids. As gelling and polymer separation occur in aircraft de-icing fluids especially during storage, the loss of the bulk fluid viscosity may render -the de-icer ineffective as an anti-icing agent. Clearly there is a need to stabilize such a system from gelling. `
The present invention is directed towards the provision of a microemulsion of oil in a water/glycol solution for a synergistically thickened de-icing and anti-icing composition having improved storage stability, as well as desirable shear stability, thermal stability and rheological properties.
The present invention also is directed towards the provision of an aircraft de-icing and anti-icing composition having improved storage stability as well as a desirable shear stability, thermal stability and rheological properties.
In accordance with one aspect of the present invention, there is provided a de-icing and anti-icing composition, comprising a microemulsion having a continuous phase and a discontinuous phase, the continuous phase comprising:
(a) from 5% to 85% by weight based on the weight of the total composition of a glycol, and (b) from 5% to 95% by weight of water based on the weight of the total composition;
the discontinuous phase comprising:
from 0.01% to 5.0% by weight based on the total weight ~;
of the composition of a water insoluble oil, the oil comprising carboxylic acid having from 10 to 18 carbon atoms in an amount of an 0.1 to 2.5% by weight, based on the total weight of composition, and the remainder of the composition comprising:
(c) from 0.05% to 10.0% by weight based on the ~
weight of the total composition of a -thickening agent selected from the group consisting of natural and artificial gums, cellulose ethers, carboxymethylcellulose and ~ -~
hydroxyethylcellulose, and (d) an emulsifier selected from the group ~
consisting of anionic surfactants and `-non-ionic surfactants and mixtures thereof, - `~
said emulsifier being present in an amount of from 0.1 times to 100 times the concentration - ~-of the water insoluble oil, and - ~-(e) from 0.1% to 2.5% by weight of alkanolamines based on the weight of the total composition, - ~
the total composition having a pH of from 6 to - -The compositions of this invention are in the ~ ;
form of a microemulsion. The term "microemulsion" `~
connotes that the composition appears clear but the ;~
occluded phase (i.e., the non-continuous phase) is still able to effect the refraction of light. Generally, the - ;-occluded phase has droplet sizes less than 0.5 microns in diameter and in many instances the occluded phase :
i~1084 comprises micelles. Microemulsions are characterized by having the oil dispensed in mlcro-droplets in the aqueous solution so that these droplets are smaller than the wavelength of visible light and consequently the microemulsion appears transparent. Procedures for preparing microemulsions are fully described in the textbook "Microemulsion Theory and Practice", Leon M.
Prince, Editor (Academic Press, Inc. 1977).
Advantageous compositions of this invention provide excellent de-icing and anti-icing properties, shear stability, and rheological properties such that the compositions are readily removed from the aircraft surfaces during takeoff, even at temperatures below O.C, - -e.g., to -20.C. Moreover, the properties of the compositions are not unduly affected by evaporation of water after application to a surface. The compositions also exhibit good storage stability, particularly with the composition using xanthan gum thickening agents.
The compositions of the present invention are characterized by a continuous phase comprising water and glycols meaning that the water/glycols phase extends through all parts of the microemulsion in a continuous fashion. This combination can vary from a water concentration of from 25% to 95% by weight based on the total weight of the composition. The preferred water composition range for the de-icer and anti-icer composition is from 40% to 50% by weight of the total composition.
The glycols useful in the continuous phase composition include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and mixtures thereof.
The oil which forms the discontinuous phase of the composition includes, but is not limited to, non-polar and partially polar, alipbatic and aromatic oils, such as mineral oil, paraffin oil, silicone oil, ~ : : ' ~
.: ~ .
' - ~
- 1~3108~ : ~
propylene oxide/ethylene oxide copolymers as well as sulfated, sulfonated, phosphated and phosphonated oils and the like. The oil comprises a carboxylic acid -; -having from 10 to 18 carbon atoms in the amount of from 0.1 to 2.5% by weight based on the total weight of composition. The amount of such oil present in the ;
microemulsion with the continuous phase components of the composition of this invention should be in the range - ~ -of from 0.01% to 5.0% by weight based on the total weight of the composition. The preferred range is 0.1%
to 1.0% by weight based on the total weight of the invention.
The water soluble thickening agent useful in :
the present invention to improve the anti-icing -characteristics of the composition includes starches, --modified starches and starch derivatives, as well as -natural and artificial gums, cellulose ether, ~ -carboxymethylcellulose, hydroxyethylcellulose, ; - -~
methylcellulose and their derivatives, ethylene oxide/
proplyene oxide copolymers, polyvinyl alcohol and their - ;;
related products. The amount of such thickening agent ~ - -can vary from 0.05% to 10.0% by weight based on the ~ ~-total weight of the composition. The preferred ranged is from 0.05% to 5% by weight based on the total weight of the composition. ; ;~
The emulsifiers used in the present composition can include any of a wide range of anionic surfactants, such as organo-phosphates, phonphonates, ~-sulfates and sulfonates, as well as fatty acid salts and non-ionic surfactants, such as alcohols, phenols, ;
amines, fatty acids and their alkoxylated derivatives and the like. The above anionic and non-ionic surfactants can be used singly or preferably in a combination of at least two surfactants, to facilitate microemulsification. The amount of emulsifier required to produce the desired microemulsion is from 0.1 times ~A : -:
,. .
.
- 1331~
to about loo times the concentration by weight of the oil present in the composition. The preferred range is from about 2 times to 20 times the concentration by weight of the oil.
The composition of the present invention is blended into a microemulsion in order that the de-icing and anti-icing composition will maintain storage stability, clarity and flow characteristics even when stored under the freezing temperatures that prevail in aircrat hangers in northern climates during the winter months.
The de-icing and anti-icing composition of this invention should have a pH of between 6 and 10 with a preferred range between 7 and 9. Buffers can be included in the composition to provide this pH range.
Suitable buffers include, but are not limited to, borates, phosphates, carbonates, benzoates or mixtures thereof. Such buffer, if used, preferably is employed in an amount of between 0.1% to 2.0% by weight of the total composition.
One minor additive that is particularly desirable is a defoamer in view of the substantial ~
quantities of emulsifier employed in the composition. -Any commercially available defoamer or anti-foamer can -be used, but a particularly preferred defoamer is a silicone defoamer of Union Carbide sold under the trade , mark SAG. The amount of this defoamer to be used is preferably in the range of from 0.05% to 0.5% by weight -based on the weight of the total composition. -~
The anti-icing property of the invention can be measured by the use of the following procedure. A
mixture of ethylene glycol and water at a ratio of 88:12 -~ -is used as a reference material because of its known - ;~
anti-icing property. Under the set condition of -8~C
and at a precipitation rate of 1.08 mm/hr, the : '.
,':, '~: ~'~
' ~:: ' . ~ ~ '', ' ' ,- 13310~
, . ,, .- .
reference material was measured to have 15 minutes of ~ -anti-icing time.
As an illustration, both the reference material and a composition of the present invention were applied to the surfaces of two separate aluminum panels cooled to -20C. A mist of freezing water then was - ~
sprayed onto the surfaces until frostication occurred in --both cases. The times elapsed were recorded. Based on the 15 minute anti-icing protection time of the reference material, the protection time of the invention composition could be calculated.
While the anti-icing time of any composition varied as a function of the temperature and ;~
precipitation rates, it was estimated that a de-icing, anti-icing fluid of a yield value of 1 dyne/cm2 would -give approximately 2 hours of anti-icing protection ~; ;;
under the temperature and precipitation conditions as -mentioned above. The yield value is defined as the minimum amount of force required to initiate the flow of a fluid from its rest state. In general practice, it can be approximated by the use of Brookfield LVT
viscosities. -~
The following Examples of de-icing and anti-icing compositions of the present invention are set forth for purposes of illustration, but are in no way intended to limit the scope of the invention.
:;,, ', ExamDle 1 ~ , A microemulsion composition of the invention -was prepared by mixing ethylene glycol, water and mineral oil vigorously at up to 70C, together with the other components, to form the de-icer and anti-icing composition. The microemulsion was allowed to cool slowly to room temperature (25C). The resulting product had a clear bright appearance and contained the following components in percentages by weight based on '.
:, ., .
, the total weight of the composition:
(a) 84.0% ethylene glycol (b) 2.0% dipotassium hydrogen phosphate~
(c) 0.1% xanthan gum (d) 6.9% water ~ (e) 1.0% white mineral oil 10 cst ^~ (f) 1.5% carboxylic acid having from 10-18 carbonatoms -.
(g) 1.5% triethanolamine (h) 3.0% of a mixture of non-ionic surfactants of Example 2 A ~icroemulsion was prepared to demonstrate the synergistics of the following components, the percentages given are percents by weight based on the : r total weight of the composition:
(a) 40.0% ethylene glycol (b) 14.0% diet ffl lene glycol (c) 41.7% water (d) 2.0% dipotassiu~ hydrogen phosphate :
(e) 0.1% xanthan gum (f) 0.25% mineral oil (g) 1.0% carboxylic acid having from 10-18 carbon -~
. 25 atoms ~ (h) 0.7% triethanolamine :~ (i) 0.25% of a mixture of non-ionic surfactants of H~3 5-14 .-~-The yield value of the de-icing and anti-icing agent at -S-C in the absence of components - (f) through (j) was found to be 0.14 dyne/cm2 while a compo~ition containing all of the ~bove compononts gives a yield value of 1.0 dyno/cm2 under the ~ame tomperature conditions. This corr-~ponds to a significant `~
D
133108~
improvement in rheological properties due to the synergistic activity between the xanthan gum and the microemulsion. The yield value is defined as the minimum amount of force required to initiate the flow of a fluid from its rest state. In general practice, it can be approximated by the use of Brookfield LVT
viscosities . , Example 3 lo A de-icing and anti-icing composition containing silicone oil was prepared by mixing the following components in a microemulsion. Again, the amounts are in percent by weight based on the total weight of the composition: - -(a) 40.0% ethylene glycol (b) 14.0% diethylene glycol (c) 41.4% water (d) 0.1% xanthan gum (e) 0.2% tolyltriazole - -(f) 1.0% carboxylic acid having from 10 to 18 carbon atoms (g) 1.0% triethanolamine (h) 1.0% of a mixture of non-ionic surfactants of (i) 0.3% potassium hydroxide (j) 1.0% dimethyl polysiloxane (10-20 cSt) This composition had substantially the same yield value as in Example 2.
Example 4 A de-icing and anti-icing composition similar ~
to the sample prepared in Example 3 can be obtained by ~ ~ :
replacing the dimethyl polysiloxane with 0.25% by weight of propylene oxide based synthetic oil of 300 SUS ;
viscosity to give the same magnitude of synergistic thickening activity as in Example 2.
,. -1 33108~
Example 5 Another composition containinq anionic surfactants was prepared by mixing the following components in a microemulsion: ~
(a) 36.0% ethylene glycol -:
(b) 18.0% diethylene glycol :
(c) 42.27% water (d) 0.3% potassium hydroxide :~
(e) 0.2% tolyltriazole ~ :
(f) 0.13% xanthan gum -:
(g) 1.0% carboxylic acid having from 10 to 18 carbon atoms :
(h) 1.0% triethanolamine (i) 0.5% sodium arylalkylsulfonate :.
(j) 0.5% phosphorester 600 anionic surfactant (k) 0.1% mineral oil The yield value calculated based on the Brookfield viscosities at -5 C is 1.26 dyne/cm2.
Example 6 A de-icer and anti-icing composition having a : relatively high yield value of 17.0 dyne/cm2 was :~
prepared by use of the following components in percent by weight based on the total weight of the composition : ~ m-:~
to demonstrate the increase in shear stability of the ~` microemulsified fluid: .`~
(a) 36.0% ethylene glycol ~ ;s:~
(b) 18.0% diethylene glycol (c) 41.95% water :: ~ -(d) 0.3% potassium hydroxide ~ :
(e) 0.2% tolytriazole - (f) 0.3% xanthan gum .
(g) 1.0% carboxylic acid having 10-18 carbon atoms : 35 (h) 1.0% triethanolamine ~ ;
: ' . :,'.: "~:, ~
133108~
(i) 1.0% of a mixture of non-ionic surfactants of (j) 0.25% mineral oil . :
When sheared by the use of a Brookfield counter-rotating mixer for 5 minutes at 3500 rpm, the .
yield value reduced to 14.4 dyne/cm2 while the composition without microemulsion gives a yield value of :
only 12 dyne/cm2.
Exam~le 7 A similar composition to that described in Example 6 was prepared by microemulsifying the following ~ -components in percent by weight based on the total weight of the composition to demonstrate the synergistic thickening activity using a water soluble polymer other than xanthan gum:
(a) 40.0% ethylene glycol -(b) 14.0% diethylene glycol ~ ~
(c) 41.65% water - ~ :
(d) 0.3% potassium hydroxide ~ ~:
(e) 0.2% benzotriazole (f) 0.5% carboxy methyl cellulose : ;
(g) 1.0% carboxylic acid having 10-18 carbon atoms (h) 1.0% triethanolamine (i) 1.0% of a mixture of non-ionic surfactants of HLB 5-14 . .
(j) 0.35% mineral oil ~
,, The yield value of the composition in the ~ ~;
absence of components (g) through (j) at -18~C is zero.
While incorporating components (g) to (j) gives a value , .
of 0.40 dyne/cm2. The use of the microemulsion with the ~ :
mineral oil, carboxylic acid and other components has in . ~ -~
fact rendered thilotropic property to the polymer in the water/glycol solution. : :
,_, , . `' '5 '`'.` . " " ' " ~ '' ' " '~ ' ' " '' 1331n~a SUPPLEMENTARY DISCLOSURE
The principai specification describes de-icer and anti-icing compositions consisting of a microemulsion having a continuous phase and a discontinuous phase and comprising a variety of components. Certain~~pecific -~
~ Examples of suitable compositions are described.
~~ The following Table I sets forth additional compositions of this invention that have desirable de-icing and anti-icing properties and advantageous rheological properties with shear stability and storage stability: ~
TABLE I ~-(all percentages are by weight based on the total composition) - -Composition Composition Composition Com~ound A % B % C %
Monoethylene glycol 36 37 - -Diethylene glycol 18 18 Triethylene glycol - - 55 - ~ -Water 42.3 41.9 41.87 - ~ ---Xanthan Gum 0.13 0.1 0.1 -Ammonium polyacrylate 0.5 - -Isosteric Acid 1.0 1.0 1.0 ~
Triethanol Amine 1.0 1.0 1.0 ~ --Non-ionic surfactants, HLB 5-14 1.0 1.0 1.0 Potassium hydroxide (so%) 0.06 0.04 0-04 .. : ~ :. :-One component of the composition of the invention is a glycol. Mentioned in the principal disclosure as useful glycols are ethylene glycol, ! diethylene glycol, ~ropylene glycol, dipropylene glycol and mixtures thereof. Other useful glycols include triethylene glycol and glycerol, which may be employed in adm$xture with each other or with the glycols described in the principal disclosure. See, for D
instance, U.S. Patents nos. 2,373,727; 3,940,389 and 4,358,389.
Another essential component of the compositions of the invention as described i~ the 5~ principal disclosure is from 0.01 to 5.0% by ~eight of a ~ -_ water-insoluble oil, which is described in the principal disclosure as including a carboxylic acid having from 10 -to 18 carbon atoms. In accordance with this supplementary disclosure, the discontinuous phase may comprise up to 5.0% (preferably at least about 0.01%) by weight of the total composition of the water-insoluble -oil and such water-insoluble oil may comprise at least one substantially water-insoluble, partially polar ~ -compound in an amount of from 0.1 to 2.5% by weight based on the weight of the total composition.
Such polar compounds include carboxylic acids, sulfuric acids, phosphoric acids, salts and polar esters thereof having hydrocarboxyl substituents of at least about 6, often 10 to 40, eg. 10 to 18, carbon atoms per polar group. In addition to the carboxylic acids having from 10 to 18 carbon atoms described in the prin-cipal disclosure, preferred water-insoluble partially polar compounds include hydrocarboxyl-substituted polyacrylate in which the hydrocarboxyl substituents have from about 6 to 40 carbon atoms. Generally, the molecular weight of the hydrocarboxyl-substituted polyacrylates is less than about 100,000, say about 700 to 50,000.
The partially polar compounds will usually comprise a microemulsion of micelles. The addition of ;
further water insoluble oils generally leads to an increase in the micelle size.
Claims
1. A de-icer and anti-icing composition comprising a microemulsion having a continuous phase and a discontinuous phase, said continuous phase comprising:
a) from 5% to 85% by weight based on the weight of the total composition of a glycol selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and mixtures thereof, and b) from 5% to 95% by weight of water based on the weight of the total composition;
said discontinuous phase comprising:
from 0.01 to 5.0% by weight based on the total weight of the composition of a water insoluble oil, said oil comprising a carboxylic acid having from 10 to 18 carbon atoms in an amount of from 0.1 to 2.5% by weight based on the total weight of composition, and the remainder of the composition comprising:
c) from 0.05% to 10.0% by weight based on the weight of the total composition of a thickening agent selected from the group consisting of natural and artificial gums, cellulose ethers, carboxymethylcellulose and hydroxyethylcellulose, d) an emulsifier selected from the group consisting of anionic surfactants and non-ionic surfactants and mixtures thereof, said emulsifier being present in an amount of from 0.1 times to 100 times the concentration of the water insoluble oil, e) from 0.1% to 2.5% by weight of alkanolamines based on the weight of the total composition;
said total composition having a pH of from 6 to 10.
3. A composition as claimed in claim 1 wherein:
i) the glycol is present in an amount of from 40%
to 60% by weight based on the weight of the total composition, ii) said water is present is an amount of from 40%
to 50% by weight, iii) said water insoluble oil is present in an amount of from 0.1% to 1.0% by weight, iv) said thickening agent is present in an amount of from 0.1% to 5.0% by weight, and v) said emulsifier is present is an amount of between 2.0 times to 20.0 times the concentration by weight of said water insoluble oil.
4. A composition as claimed in claim 3 wherein said glycol is ethylene glycol and wherein said water insoluble oil comprises mineral oil.
5. A composition as claimed in claim 3 wherein thickening agent is xanthan gum.
6. A composition as claimed in claim 3 wherein said emulsifier is a non-ionic surfactant.
7. A composition as claimed in claim 6 wherein the non-ionic surfactant provides an HLB of 5 to 14.
8. A composition as claimed in claim 1 having a pH of from 7 to 9.
9. A composition as claimed in claim 1 further comprising a defoamer.
CLAIMS SUPPORTED BY SUPPLEMENTARY DISCLOSURE
10. The composition of claim 1 wherein said glycol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol and mixtures thereof.
11. A de-icer and anti-icing composition comprising a microemulsion having a continuous phase and a discontinuous phase, said continuous phase comprising:
a) from 5% to 85% by weight based on the weight of the total composition of a glycol selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol and mixtures thereof, and b) from 5% to 95% by weight of water based on the weight of the total composition;
said discontinuous phase comprising from 0.01 to 5.0% by weight based on the total weight of the composition of a water insoluble oil, the oil comprises at least one substantially water-insoluble, partially polar compound in an amount of from 0.1% to 2.5% by weight based on the weight of the total composition, and the remainder of the composition comprising:
c) from 0.05% to 10.0% by weight based on the weight of the total composition of a thickening agent selected from the group consisting of natural and artificial gums, cellulose ethers, carboxymethylcellulose and hydroxyethylcellulose, d) an emulsifier selected from the group consisting of anionic surfactants and non-ionic surfactants and mixtures thereof, said emulsifier being present in an amount of from 0.1 times to 100 times the concentration of the water insoluble oil, and e) from 0.1% to 2.5% by weight of alkanolamines based on the weight of the total composition;
said total composition having a pH of from 6 to 10.
12. A composition as claimed in claim 11 wherein the partially polar compound comprises at least one of carboxylic, sulfuric and phosphoric acids, salts or polar esters having hydrocarbyl substituents of at least about 6 carbon atoms per polar group.
13. A composition as claimed in claim 11 wherein the partially polar compound comprises a hydrocarboxyl substitute of polyacrylate in which the hydrocarboxyl substituent has from about 6 to 40 carbon atoms.
14. A composition as claimed in claim 11 wherein:
i) the glycol is present in an amount of from 40%
to 60% by weight based on the weight of the total composition, ii) said water is present in an amount of from 40%
to 50% by weight, said water insoluble oil comprises carboxylic acid and is present in an amount of from 0.1% to 1.0% by weight, iii) said thickening agent is present in an amount of from 0.1% to 5.0% by weight, and iv) said emulsifier is present in an amount of between 2.0 times to 20.0 times the concentration by weight of said water insoluble oil.
15. A composition as claimed in claim 14 wherein said water insoluble oil comprises mineral oil.
16. A composition as claimed in claim 11 wherein thickening agent comprises xanthan gum.
17. A composition as claimed in claim 11 wherein the emulsifier comprises non-ionic surfactant.
18. A composition as claimed in claim 17 wherein the non-ionic surfactant provides an HLB of 5 to 14.
19. A composition as claimed in claim 11 having a pH of from 7 to 9.
20. A composition as claimed claim 11 further comprising a defoamer.
a) from 5% to 85% by weight based on the weight of the total composition of a glycol selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and mixtures thereof, and b) from 5% to 95% by weight of water based on the weight of the total composition;
said discontinuous phase comprising:
from 0.01 to 5.0% by weight based on the total weight of the composition of a water insoluble oil, said oil comprising a carboxylic acid having from 10 to 18 carbon atoms in an amount of from 0.1 to 2.5% by weight based on the total weight of composition, and the remainder of the composition comprising:
c) from 0.05% to 10.0% by weight based on the weight of the total composition of a thickening agent selected from the group consisting of natural and artificial gums, cellulose ethers, carboxymethylcellulose and hydroxyethylcellulose, d) an emulsifier selected from the group consisting of anionic surfactants and non-ionic surfactants and mixtures thereof, said emulsifier being present in an amount of from 0.1 times to 100 times the concentration of the water insoluble oil, e) from 0.1% to 2.5% by weight of alkanolamines based on the weight of the total composition;
said total composition having a pH of from 6 to 10.
3. A composition as claimed in claim 1 wherein:
i) the glycol is present in an amount of from 40%
to 60% by weight based on the weight of the total composition, ii) said water is present is an amount of from 40%
to 50% by weight, iii) said water insoluble oil is present in an amount of from 0.1% to 1.0% by weight, iv) said thickening agent is present in an amount of from 0.1% to 5.0% by weight, and v) said emulsifier is present is an amount of between 2.0 times to 20.0 times the concentration by weight of said water insoluble oil.
4. A composition as claimed in claim 3 wherein said glycol is ethylene glycol and wherein said water insoluble oil comprises mineral oil.
5. A composition as claimed in claim 3 wherein thickening agent is xanthan gum.
6. A composition as claimed in claim 3 wherein said emulsifier is a non-ionic surfactant.
7. A composition as claimed in claim 6 wherein the non-ionic surfactant provides an HLB of 5 to 14.
8. A composition as claimed in claim 1 having a pH of from 7 to 9.
9. A composition as claimed in claim 1 further comprising a defoamer.
CLAIMS SUPPORTED BY SUPPLEMENTARY DISCLOSURE
10. The composition of claim 1 wherein said glycol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol and mixtures thereof.
11. A de-icer and anti-icing composition comprising a microemulsion having a continuous phase and a discontinuous phase, said continuous phase comprising:
a) from 5% to 85% by weight based on the weight of the total composition of a glycol selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol and mixtures thereof, and b) from 5% to 95% by weight of water based on the weight of the total composition;
said discontinuous phase comprising from 0.01 to 5.0% by weight based on the total weight of the composition of a water insoluble oil, the oil comprises at least one substantially water-insoluble, partially polar compound in an amount of from 0.1% to 2.5% by weight based on the weight of the total composition, and the remainder of the composition comprising:
c) from 0.05% to 10.0% by weight based on the weight of the total composition of a thickening agent selected from the group consisting of natural and artificial gums, cellulose ethers, carboxymethylcellulose and hydroxyethylcellulose, d) an emulsifier selected from the group consisting of anionic surfactants and non-ionic surfactants and mixtures thereof, said emulsifier being present in an amount of from 0.1 times to 100 times the concentration of the water insoluble oil, and e) from 0.1% to 2.5% by weight of alkanolamines based on the weight of the total composition;
said total composition having a pH of from 6 to 10.
12. A composition as claimed in claim 11 wherein the partially polar compound comprises at least one of carboxylic, sulfuric and phosphoric acids, salts or polar esters having hydrocarbyl substituents of at least about 6 carbon atoms per polar group.
13. A composition as claimed in claim 11 wherein the partially polar compound comprises a hydrocarboxyl substitute of polyacrylate in which the hydrocarboxyl substituent has from about 6 to 40 carbon atoms.
14. A composition as claimed in claim 11 wherein:
i) the glycol is present in an amount of from 40%
to 60% by weight based on the weight of the total composition, ii) said water is present in an amount of from 40%
to 50% by weight, said water insoluble oil comprises carboxylic acid and is present in an amount of from 0.1% to 1.0% by weight, iii) said thickening agent is present in an amount of from 0.1% to 5.0% by weight, and iv) said emulsifier is present in an amount of between 2.0 times to 20.0 times the concentration by weight of said water insoluble oil.
15. A composition as claimed in claim 14 wherein said water insoluble oil comprises mineral oil.
16. A composition as claimed in claim 11 wherein thickening agent comprises xanthan gum.
17. A composition as claimed in claim 11 wherein the emulsifier comprises non-ionic surfactant.
18. A composition as claimed in claim 17 wherein the non-ionic surfactant provides an HLB of 5 to 14.
19. A composition as claimed in claim 11 having a pH of from 7 to 9.
20. A composition as claimed claim 11 further comprising a defoamer.
Priority Applications (16)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PT85614A PT85614B (en) | 1986-08-28 | 1987-08-27 | PROCESS FOR THE PREPARATION OF ANTIFREEZE AND ANTIGEL COMPOSITIONS FOR AIRCRAFT |
| AU77623/87A AU594187B2 (en) | 1986-08-28 | 1987-08-27 | Aircraft de-icing and anti-icing compositions |
| FI873716A FI89273C (en) | 1986-08-28 | 1987-08-27 | BLACKING FOR OVERFLOWING FORWARDING WITH FLYGMASKINER |
| DE8787201618T DE3774966D1 (en) | 1986-08-28 | 1987-08-27 | DEFROSTING AND ICE PREVENTING COMPOSITION FOR AIRCRAFT. |
| IS3254A IS1550B (en) | 1986-08-28 | 1987-08-27 | Mix for the defense and de-icing of aviation |
| CN87106033A CN1011513B (en) | 1986-08-28 | 1987-08-27 | Aircraft de-icing and anti-icing compositions |
| AT87201618T ATE70078T1 (en) | 1986-08-28 | 1987-08-27 | DEFROST AND ANTI-ICING COMPOSITION FOR AIRCRAFT. |
| NO873622A NO873622L (en) | 1986-08-28 | 1987-08-27 | FLIGHT DISPOSAL AND PREVENTION PREPARATION. |
| NZ221595A NZ221595A (en) | 1986-08-28 | 1987-08-27 | De-icing and anti-icing compositions |
| JP62211533A JPH0674408B2 (en) | 1986-08-28 | 1987-08-27 | Deicing and anti-icing composition for aircraft |
| KR1019870009372A KR930002222B1 (en) | 1986-08-28 | 1987-08-27 | Aircraft de-icing and anti-icing compositions |
| EP87201618A EP0257720B1 (en) | 1986-08-28 | 1987-08-27 | Aircraft de-icing and anti-icing composition |
| DK447987A DK447987A (en) | 1986-08-28 | 1987-08-27 | DEPOSITING AND PROTECTION PROTECTION DEPARTMENTS |
| ES198787201618T ES2026900T3 (en) | 1986-08-28 | 1987-08-27 | DEFROSTING FOR AIRCRAFT AND ANTIFREEZE COMPOSITIONS. |
| US07/153,212 US4954279A (en) | 1986-08-28 | 1988-02-08 | Aircraft de-icing and anti-icing composition |
| GR910401175T GR3003947T3 (en) | 1986-08-28 | 1992-03-04 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/153,212 US4954279A (en) | 1986-08-28 | 1988-02-08 | Aircraft de-icing and anti-icing composition |
| US153,212 | 1988-02-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1331084C true CA1331084C (en) | 1994-08-02 |
Family
ID=22546235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 517026 Expired - Fee Related CA1331084C (en) | 1986-08-28 | 1986-08-28 | Aircraft de-icing and anti-icing composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1331084C (en) |
-
1986
- 1986-08-28 CA CA 517026 patent/CA1331084C/en not_active Expired - Fee Related
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