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    • 专利摘要:
    Hygrometer sensor based on a collagen material. The present invention relates to a hygrometer sensor comprising: A) between 35% and 60% by weight with respect to the total weight of the sensor of a collagenic material selected from collagen foil and skin; B) between 2% and 20% by weight with respect to the total weight of the sensor of at least one ionic surfactant; C) between 30% and 60% by weight with respect to the total weight of the sensor of at least one nonionic surfactant; With the proviso that the percentages of the different sensor components are such that the total does not exceed 100%. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2558846A1
    申请号:ES201431019
    申请日:2014-07-07
    公开日:2016-02-09
    发明作者:Fernando MALDONADO MILLÁN；Albert María MANICH BOU；José CARILLA AUGUET；Agustín MARSAL MONGE
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

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    Hygrometric sensor based on a collagenic material.
    The present invention relates to a moisture gravimetric sensor, therefore, the present invention can be framed in the technical field of measuring instruments, in particular hygrometers.
    STATE OF THE TECHNIQUE
    The precise determination of the relative humidity is of great importance in meteorology, in the control of laboratory humidity, in heated chambers, in areas of manufacture of pure materials, particularly when their manufacture must be carried out in a controlled atmosphere, in storage of products and in libraries, archives and museums where goods of cultural interest are preserved. It is also interesting to control humidity in greenhouses, saunas, residences and other premises.
    The humidity measurement procedures are very diverse, are applied under different conditions and must be able to determine the humidity of the environment with the precision required in each case, covering the entire range of variation from 0 to 100% relative humidity (HR).
    Except for rockpoint hygrometers, there is no procedure that covers the entire measuring range with sufficient precision. In conditions close to saturation, condensations occur which, depending on the type of sensor, disturb its operation and mask the results. If to avoid condensation, the temperature of the sensor is increased, the relative humidity values are altered, forcing the sensor to recalibrate to the new temperature to obtain reliable measurements. The rock point hygrometers with a refrigerated mirror can measure the rock point independently of the air temperature. If this is known, the% RH of the air can be calculated. The cost of the system is high and its size does not allow its use in small spaces. It is generally used in calibration of other measurement systems.
    Hygrometers or humidity sensors base their operation on the use of a sensor that has a characteristic sensitive to the relative humidity variation of the environment in which it is located. This can be from the temperature decrease of a thermometer with a wet bulb due to evaporation (psychrometer), to the determination of the temperature of the air cycle or the variation in length, mass, electrical characteristics (resistance, capacity, impedance) , absorption (lyman-alpha), or using natural, electrolytic or mesoporous synthetic materials with large contact area (83.2 m2 / g) that vary their impedance with the water content (J Zhao et al. Sensors and Actuators B, 2013, 181, 802-809).
    Each procedure has its limitations. Hygrometers based on length measurements can lead to drifts of up to 20-30% of the initial calibration. The psychrometers cannot work at temperatures below 0 ° C, they work in an acceptable way for humidities between 15 and 100% RH but their sensitivity depends on the air flow for the evaporation of the wet bulb and the state of cleanliness thereof. The capacitive sensors have a good response between 10 and 95% RH, the resistives have more limited ranges and those of rock point depend on the skill of the operator and have the limitation of their cost and their dimensions.
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    Gravimetric hygrometers, described so far, that base the measurement of humidity on the variation of the sensor's mass, can give reproducible results over the entire humidity range (0 to 100% RH) although they have a limitation in relation to accuracy of the results, because of the phenomenon of hysteresis that occurs by coalescence inside the pores. The moisture content of the material in equilibrium situation depends on the previous humidity conditions from which it comes. If it was in a drier environment, the mass in the balance would be lower than that obtained if it came from a more humid environment. This difference affects the accuracy with which the ambient humidity can be determined.
    Thus, there is still a need to develop sensors that respond reliably to the entire range of humidity variation, in particular relative humidity near 0% and 100% and that do not show hysteresis.
    In previous works of the inventors, the sorption and desorption of a monolayer of water in skin and skin powder was studied using the BET models (Brunauer, Emmett and Teller) and GAB (Guggenheim, Andersen and de Boer) (J.Am Leather Chemist Assoc 2010, 105, 229-241). Although the phenomenon of hysteresis is reduced in skin powder, this material presents a serious inconvenience of manipulation and utilization as a gravimetric sensor for humidity control, since the need to be in direct contact with the environment the humidity of which wants to measure, can not avoid situations of loss of mass in handling that may occur and that invalidate its use.
    DESCRIPTION OF THE INVENTION
    The present invention relates to a hygrometric sensor based on a collagenic material suitably treated with surfactants for application as gravimetric hygrometers. It also refers to the procedure for obtaining it.
    The sensors of the present invention have the following advantages over the state of the art sensors:
    • It has very good sensitivity in the entire humidity range (0 to 100% RH), in particular at very high or very low relative humidity, without disturbances.
    • Improves the accuracy of the results obtained in gravimetric procedures that use hygroscopic materials by having eliminated the hysteresis phenomenon through treatment with surfactants.
    • It faithfully reproduces the humidity variations of hygroscopic materials when they experience changes in ambient humidity, which facilitates the monitoring and temporary control of changes in environmental conditions.
    • Provides a valid measurement procedure regardless of the ambient temperature.
    • It has a long duration, is capable of being recalibrated and is resistant to environmental contamination.
    • It is a low cost sensor with simple implementation in a gravimetric system for measuring ambient humidity.
    Therefore, a first aspect of the present invention relates to a hygrometric sensor comprising:
    a) between 35% and 60% by weight with respect to the total sensor weight of a collagen material selected from collagen and skin lamina;
    b) between 2% and 20% by weight with respect to the total weight of the sensor of at least one ionic surfactant for each part by weight of the collagenic material;
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    c) between 30% and 60% by weight with respect to the total weight of the sensor of at least one non-ionic surfactant for each part by weight of the collagenic material,
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%;
    where the ionic surfactant is selected from sulfates and halides of (C6-C30) alkylpyridinium, sulfates and halides of (C6-C30) quaternary alkylammonium, sulfates and halides of (C6-C30) alkylimidazolinium and alkaline and alkaline earth salts of (C6-C30 ) alkylsulfate, (C6-C30) alkylene ether sulfate, (C6-C30) alkylsulphonate, (C6-C30) alkylbenzenesulfonate, (C6-C30)
    alkylcarboxylate, (C6-C30) alkylethercarboxylate and (C6-C30) alkylsarcosinate and any mixture thereof;
    where the non-ionic surfactant is selected from (C6-C30) polyalkoxylated alcohols, (C6-C30) polyalkoxylated alkylphenols, (C6-C30) polyalkoxylated fatty acids, esters of polyalkoxylated fatty acids, (C6-C30) alkanolamides and (C6-C30 ) alkyl polyglucosides and any of their mixtures;
    and where the collagenous material has a thickness between 20 pm and 1000 pm.
    Hygrometric sensor is understood in the context of the present invention that material capable of absorbing and desorbing moisture from the surrounding environment, and which can be used as a hygroscopic sensor, that is, to measure the variation of relative humidity.
    By collagenic material, it is understood in the context of the present invention any material made from animal skin, whose main component is collagen.
    Collagen sheet means a sheet obtained from the extrusion of partial collagen hydrolysates from animal skin, which is mainly used as an edible wrap in the food industry.
    In the context of the present invention, skin is understood as an animal skin subjected to conventional riverbank operations (soaking, waxing, liming and rendering), pickling and degreasing prepared to be subjected to a tanning process.
    An ionic surfactant is a surfactant whose hydrophilic part has a positive or negative charge. In the context of the invention, "ionic surfactant" means a cationic or anionic surfactant. The ionic surfactants are selected from sulfates and halides of (C6-C30) alkylpyridinium, sulfates and halides of (C6-C30) quaternary alkylammonium, sulfates and halides of (C6-C30) alkylimidazolinium and alkaline and alkaline earth salts of (C6-C30) alkylsulfate, (C6-C30) alkylene ether sulfate, (C6-C30) alkylsulphonate, (C6-C30) alkylbenzenesulfonate, (C6-C30) alkylcarboxylate, (C6-C30) alkylcarboxylate and (C6-C30) alkylsarcosinate and any mixtures thereof, such as for example hexadecylpyridinium chloride (CHP), hexadecyltrimethylammonium chloride, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecyl ether sulfate, sodium dodecyl sulphonate, sodium lauryl carboxylate, sodium dodecyl ether carboxylate and sodium lacyl.
    A non-ionic surfactant is a surfactant that does not comprise dissociable (ionizable) functional groups and therefore does not dissociate in the water into ions. The polar groups that make up one of the parts of the surfactant are usually alcohol and ether groups. The non-ionic surfactants of the invention are selected from (C6-C30) polyalkoxylated alcohols, (C6-C30) polyalkoxylated alkylphenols, (C6-C30) polyalkoxylated fatty acids, esters of polyalkoxylated fatty acids, (C6-C30) alkanolamides and (C6 -C30) alkyl polyglucosides and any of their
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    mixtures, the polyalkoxylates being preferably polyoxyethylene and polyoxypropylene type, such as nonylphenoloxyethylene, nonylphenol with 10 moles of ethylene oxide, lauryl alcohol with 9.5 moles of ethylene oxide, polyglucopyranoside with degree of polymerization 1.3, polyglucopyranoside with degree of polymerization (grade 1.4 KAG-40).
    In an embodiment of the first aspect of the present invention, the sensor as defined above comprises:
    a) between 40% and 55% by weight with respect to the total weight of the collagen material sensor;
    b) between 5% and 15% by weight with respect to the total weight of the sensor of at least one ionic surfactant;
    c) between 35% and 55% by weight with respect to the total weight of the sensor of at least one non-ionic surfactant;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%.
    In another embodiment of the first aspect of the present invention, the thickness of the collagenous material is from 50 pm to 500 pm. The smaller the thickness of the collagen material, the less time is needed to reach equilibrium.
    In another embodiment of the first aspect of the present invention, the non-ionic surfactant is a (C8-C12) polyoxyethylene alkylphenol, preferably the non-ionic surfactant is nonylphenolpolyoxyethylene and more preferably it is nonylphenol oxyethylene with 10 moles of ethylene oxide (NFOE-10) .
    In another embodiment of the first aspect of the present invention, the non-ionic surfactant is a (C8-C15) alkyl polyglucoside, preferably the non-ionic surfactant is a mixture C9, C10, C11 alkyl polyglucopyranoside with polymerization degree 1,3 (KAG-40 ).
    In another embodiment of the first aspect of the present invention, the ionic surfactant is a cationic surfactant, preferably the cationic surfactant is selected from (C10-C20) alkylpyridinium halide, (C10-C20) alkylammonium halide and any mixture thereof, and more preferably the cationic surfactant is hexadecylpyridinium chloride.
    In an embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 35% and 60% by weight with respect to the total sensor weight of a collagen material selected from collagen and skin lamina;
    b) between 2% and 20% by weight with respect to the total weight of the halide sensor of (C10-C20) alkylpyridinium, halide of (C10-C20) alkylammonium or any of its mixtures;
    c) between 30% and 60% by weight with respect to the total weight of the (C8-C12) alkylphenol polyoxyethylene sensor;
    with the proviso that the percentages of the different components of the sensor are such that the total does not exceed 100%.
    In an embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 35% and 60% by weight with respect to the total sensor weight of a collagen material selected from collagen and skin lamina;
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    b) between 2% and 20% by weight with respect to the total weight of the hexadecylpyridinium chloride sensor;
    c) between 30% and 60% by weight with respect to the total weight of the oxyethylene nonylphenol sensor with 10 moles of ethylene oxide;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%.
    In another embodiment of the first aspect of the present invention, the ionic surfactant is an anionic surfactant, preferably the anionic surfactant is selected from alkaline or alkaline earth salts of (C10-C16) alkylsulfate, (C10-C16) alkylsulfonate and (C10-C16) alkylbenzenesulfonate and any of its mixtures, more preferably the anionic surfactant is selected from sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium tetradecylsulfonate and sodium lauroyl sarcosinate and even more preferably the anionic surfactant is sodium dodecyl sulfate.
    In an embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 35% and 60% by weight with respect to the total sensor weight of a collagen material selected from collagen and skin lamina;
    b) between 2% and 20% by weight with respect to the total weight of the sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium tetradecyl sulphonate, sodium lauroyl sarcosinate or any mixture thereof;
    c) between 30% and 60% by weight with respect to the total weight of the (C8-C12) alkylphenol polyoxyethylene sensor;
    with the proviso that the percentages of the different components of the sensor are such that the total does not exceed 100%.
    In an embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 35% and 60% by weight with respect to the total sensor weight of a collagen material selected from collagen and skin lamina;
    b) between 2% and 20% by weight with respect to the total weight of the sodium dodecyl sulfate sensor;
    c) between 30% and 60% by weight with respect to the total weight of the oxyethylene nonylphenol sensor with 10 moles of ethylene oxide;
    with the proviso that the percentages of the different components of the sensor are such that the total does not exceed 100%.
    In an embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 35% and 60% by weight with respect to the total sensor weight of a collagen material selected from collagen and skin lamina;
    b) between 2% and 20% by weight with respect to the total weight of the sodium dodecyl sulfate sensor;
    c) between 30% and 60% by weight with respect to the total weight of the sensor of a mixture C9, C10, C11 alkyl polyglucopyranoside with polymerization degree 1.3;
    with the proviso that the percentages of the different components of the sensor are such that the total does not exceed 100%.
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    In another embodiment of the first aspect of the present invention, the collagenic material is collagen sheet. Collagen-based sensors have the highest reproducibility and highest responsiveness since a smaller material thickness can be achieved.
    In another embodiment of the first aspect of the present invention, the collagen material is collagen sheet and has a thickness of 20 p, m to 500 p, m, and more preferably 50 p, m to 200 p, m.
    In a particular embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 40% and 55% by weight with respect to the total weight of the collagen material sensor, where the collagen material is collagen lamina;
    b) between 5% and 15% by weight with respect to the total weight of the hexadecylpyridinium chloride sensor;
    c) between 35% and 55% by weight with respect to the total weight of the oxyethylene nonylphenol sensor with 10 moles of ethylene oxide;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%;
    where the collagen sheet has a thickness of 20 p, m to 500 p, m, preferably 50 to 200 p, m.
    In another particular embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 40% and 55% by weight with respect to the total weight of the collagen material sensor, where the collagen material is collagen lamina;
    b) between 5% and 15% by weight with respect to the total weight of the sodium dodecyl sulfate sensor;
    c) between 35% and 55% by weight with respect to the total weight of the oxyethylene nonylphenol sensor with 10 moles of ethylene oxide;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%;
    where the collagen sheet has a thickness of 20 p, m to 500 p, m, preferably 50 to 200 p, m.
    In another particular embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 40% and 55% by weight with respect to the total weight of the collagen material sensor, where the collagen material is collagen lamina;
    b) between 5% and 15% by weight with respect to the total weight of the sodium dodecyl sulfate sensor;
    c) between 35% and 55% by weight with respect to the total weight of the sensor of a mixture C9, C10, C11 alkyl polyglucopyranoside with polymerization degree 1.3;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%;
    where the collagen sheet has a thickness of 20 p, m to 500 p, m, preferably 50 to 200 p, m.
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    In another embodiment of the first aspect of the present invention, the collagenic material is skin, preferably lyophilized skin.
    In another embodiment of the first aspect of the present invention, the collagenic material is skin, preferably lyophilized skin and has a thickness of 200 to 700 p, m, and more preferably 300 p, m to 450 p, and even more preferably 400 p, m.
    In a particular embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 40% and 55% by weight with respect to the total weight of the collagenic material sensor, where the collagenic material is lyophilized skin;
    b) between 5% and 15% by weight with respect to the total weight of the hexadecylpyridinium chloride sensor;
    c) between 35% and 55% by weight with respect to the total weight of the oxyethylene nonylphenol sensor with 10 moles of ethylene oxide;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%;
    where the lyophilized skin has a thickness of 200 p, m to 700 p, m, preferably 300 p, m to 450 p, m.
    In another particular embodiment of the first aspect of the present invention, the hygrometric sensor comprises:
    a) between 40% and 55% by weight with respect to the total weight of the collagenic material sensor, where the collagenic material is lyophilized skin;
    b) between 5% and 15% by weight with respect to the total weight of the sodium dodecyl sulfate sensor;
    c) between 35% and 55% by weight with respect to the total weight of the oxyethylene nonylphenol sensor with 10 moles of ethylene oxide;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%;
    where the lyophilized skin has a thickness of 200 p, m to 700 p, m, preferably 300 p, m to 450 p, m.
    A second aspect of the present invention relates to a method of obtaining a hygrometric sensor comprising the following steps:
    a) put in contact in water:
    i) 1 part by weight of a collagen material selected from collagen and skin lamina;
    ii) 0.05 to 0.25 parts by weight of at least one ionic surfactant for each part by weight of the collagenic material;
    iii) 0.5 to 1.8 parts by weight of at least one non-ionic surfactant for each part by weight of the collagenic material;
    b) stir between 0.5 and 24 hours;
    c) drying the collagenous material;
    where the ionic surfactant is selected from sulfates and halides of (C6-C30) alkylpyridinium, sulfates and halides of (C6-C30) quaternary alkylammonium, sulfates and halides of (C6-C30) alkylimidazolinium and alkaline and alkaline earth salts of (C6-C30 ) alkylsulfate, (C6-C30) alkylene ether sulfate, (C6-C30) alkylsulphonate, (C6-C30) alkylbenzenesulfonate, (C6-C30)
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    alkylcarboxylate, (C6-C30) alkylethercarboxylate and (C6-C30) alkylsarcosinate and any mixture thereof;
    where the non-ionic surfactant is selected from (C6-C30) polyalkoxylated alcohols, (C6-C30) polyalkoxylated alkylphenols, (C6-C30) polyalkoxylated fatty acids, esters of polyalkoxylated fatty acids, (C6-C30) alkanolamides and (C6-C30 ) alkyl polyglucosides and any of their mixtures;
    and where the collagenous material has a thickness between 20 pm and 1000 pm.
    In an embodiment of the second aspect of the present invention, in step (a) they contact:
    i) 1 part by weight of a collagen material selected from collagen and skin lamina;
    ii) 0.125 to 0.175 parts by weight of at least one ionic surfactant for each part by weight of the collagenic material;
    iii) 1 to 1.5 parts by weight of at least one non-ionic surfactant for each part by weight of the collagenic material.
    In another embodiment of the second aspect of the present invention, the thickness of the collagenous material is 50 pm and 500 pm.
    In another embodiment of the second aspect of the present invention, the non-ionic surfactant is (C8-C12) polyoxyethylene alkylphenol, preferably it is nonylphenol polyoxyethylene and more preferably it is nonylphenol oxyethylene with 10 moles of ethylene oxide (NFOE-10).
    In another embodiment of the second aspect of the present invention, the nonionic surfactant is a (C8-C15) alkyl polyglucoside, preferably the nonionic surfactant is a mixture C9, C10, C11 alkyl polyglucopyranoside with polymerization degree 1,3 (KAG-40 ).
    In another embodiment of the second aspect of the present invention, the ionic surfactant is a cationic surfactant selected from (C6-C30) alkylpyridinium sulfates and halides of (C6-C30) quaternary alkylammonium sulfates and halides of (C6-C30) alkylimidazolinium and any of its mixtures, preferably the cationic surfactant is selected from (C10-C20) alkylpyridinium halide and (C10-C20) alkylammonium halide and any of its mixtures, and more preferably the cationic surfactant is hexadecylpyridinium chloride.
    In another embodiment of the second aspect of the present invention, the ionic surfactant is a cationic surfactant and the pH of step (a) is adjusted between 9 and 13, preferably between 11 and 12.
    In another embodiment of the second aspect of the present invention, the ionic surfactant is an anionic surfactant, selected from alkaline and alkaline earth salts of (C6-C30) alkylsulfate, (C6-C30) alkylether sulfate, (C6-C30) alkylsulfonate, (C6- C30) alkylbenzenesulfonate, (C6-C30) alkylcarboxylate, (C6-C30) alkylethercarboxylate, (C6-C30) alkylsarcosinate and any mixture thereof, preferably the anionic surfactant is selected from alkaline or alkaline earth salts of (C10-C16) alkylsulfate, ( C10-C16) alkylbenzenesulfonate and any of its mixtures, more preferably the anionic surfactant is selected from sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium tetradecylsulfonate and sodium lauroyl sarcosinate and even more preferably the anionic surfactant is sodium dodecyl sulfate.
    In another embodiment of the second aspect of the present invention, the ionic surfactant is an anionic surfactant and the pH of step (a) is adjusted between 1 and 4, preferably between 2 and 3.
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    In another embodiment of the second aspect of the present invention, the collagen material is collagen sheet, preferably the collagen sheet has a thickness of 20 p, m to 500 p, m, more preferably 50 p, m to 200 p, m.
    In another embodiment of the second aspect of the present invention, the collagenic material is skin, preferably lyophilized skin.
    In another embodiment of the second aspect of the present invention, the collagenic material is skin, preferably lyophilized skin and has a thickness of 200 to 700 p, m, and more preferably 300 p, m to 450 p, and even more preferably 400 p, m.
    In another embodiment of the second aspect of the present invention, the agitation of step (b) is carried out between 1 and 10 hours.
    In another embodiment of the second aspect of the present invention, the drying of step (c) is carried out by lyophilization.
    A third aspect of the present invention relates to the hygrometric sensor obtained by the process as described above.
    A fourth aspect of the present invention refers to the use of the sensor as defined above in a gravimetric hygrometer. These hygrometers are commonly used to measure the relative humidity of the environment.
    A fifth aspect of the present invention refers to the use of the sensor as defined above to calibrate hygrometers.
    The moisture gravimetric sensor consists of a collagen or skin lamina treated with surfactants as described, conveniently calibrated so that by means of a conversion table or calculation algorithm, the environmental humidity can be determined based on the mass of the sensor. The sensor can be used in various ways, without limitation, as they refer to continuation:
    1. Simple utilization: Placed the sensor in the location where you want to measure the environmental humidity, the determination of its mass will allow to know the relative humidity of said location. This determination could be made, for example, using a calibrated dial balance where, in the quadrant, a direct reading of the relative humidity can be made.
    2. Multiple utilization: If there are several sensors, their distribution in different locations of a space, may lead to various moisture determinations at different points of that space, providing the possibility of knowing how the interior convection currents or the systems of forced air circulation may or may not alter the moisture content in different areas of an enclosure.
    3. Continuous utilization: If the calibrated sheet is coupled to a scale with continuous sensor mass recording system, using the transformation algorithm, continuous recording of the environmental mass will also be available.
    4. Uses related to the conservation of cultural heritage: In the case of muselastic enclosures or conservation of cultural heritage assets, the placement of a sensor together with a specific cultural asset of interest, allows to determine the humidity of said asset "in situ ”(Tapestry, painting, mural, library, mosaic) in a simple way without the need for complicated assemblies that alter the environment of said good.
    5. Uses related to the determination of the conditions of conservation of food or explosive materials: Conveniently located sensors can
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    Assist in the determination of the environmental humidity in which food or explosive materials can be found and whether there is a timely registration following a random sampling plan, or if continuous recording is available, this system allows to control the storage conditions of materials moisture sensitive.
    6. Calibration: The sensors can be used as calibration elements of other types of hygrometer.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1 Moisture adsorption and desorption isotherms of the collagen sheet treated with SDS + KAG-40, determined using saturated solutions of different salts to reach different levels of relative humidity (Greenspan, J.Res. Nat. Bureau Stand. A. Phys and Chem, 1977,81A, 89). The mass variation of the dried samples is represented in% (% db) as a function of the relative humidity (%).
    FIG. 2. Moisture adsorption and desorption isotherms of the skin lamina treated with SDS + NFOE-10, determined using saturated solutions of different salts to reach the different levels of relative humidity (Greenspan, 1977). The mass variation of the dried samples is represented in% (% db) as a function of the relative humidity (%).
    FIG. 3 Continuous recording of the relative humidity variation as a function of the mass of the collagen laminate sensor treated with SDS + KAG-40 for a certain period of time (5 days).
    FIGS 4 to 7. Comparative study of the effect of hysteresis without surfactants in: 3) collagen sheet, 4) skin, 5) air dried skin powder, 6) lyophilization dried skin powder (corresponding to the AD samples of the example 6)
    EXAMPLES
    The invention will be illustrated below by tests carried out by the inventors, which shows the effectiveness of the product of the invention.
    Example 1. Procedure for obtaining a hygrometric sensor based on collagen sheet.
    100 g of collagen sheet used in the meat industry supplied by the Viscofan company, 0.1 mm thick in 5 l of water, 160 g of an aqueous solution of sodium dodecyl sulfate (SDS) were introduced into a 10 l container 10% (w / w) and 1200 g of a 10% aqueous solution of oxyethylene nonylphenol with 10 moles of ethylene oxide (NFOE10). The mixture was stirred for 60 min at room temperature by rotation at a rate of 40 cycles per minute. Then, 160 ml of a 1N HCl solution was added, to obtain a pH 2.8-3, stirring for a further 6 h. After this time the sheet was removed from the solution and subjected to a 15 min suspension drain at room temperature. The sheet was cooled at -20 ° C for 24 h and underwent a lyophilization process. After conditioning the resulting sheet at room temperature it was cut into sheets of 1-3 g.
    Example 2. Procedure for obtaining a hygrometric sensor based on collagen sheet.
    5 Following the same method as in example 1, with different combinations of ionic and non-ionic surfactant, other sensors have been obtained as shown in Table 1.
    TABLE 1
     Collagenic material Ionic surfactant Non-ionic surfactant pH regulator
     2  0.1mm collagen sheet 10% hexadecylpyridinium chloride 10% NFOE NaOH (pH 11.8-12)
     3  0.1 mm collagen sheet 10% sodium dodecyl sulfate 10% KAG-40 * 1N HCl (pH 2.8-3)
     4  0.1 mm collagen sheet 10% sodium tetradecylsulfonate 10% NFOE 1N HCl (pH 2.8-3)
     5  0.1 mm collagen sheet dodecylbenzenesulfone to 10% sodium 10% NFOE 1N HCl (pH 2.8-3)
     6  0.1 mm Sodium lauroylsarcosinate 10% NFOE collagen sheet 1N HCl (pH 2.8-3)
     * mixture C9, C10, C11 alkyl polyglucopyranoside with degree of po  imerizacion 1,3
    from Kao
    10 chemicals
    Example 3. Procedure for obtaining a skin based hygrometric sensor.
    The procedure was carried out in the same manner as in Example 1 using as animal material 15,4 mm thick.
    TABLE 2
     Component  mass
     0.4 mm thick sheep skin  100g
     10% sodium dodecyl sulfate (SdS)  160 g
     10% Nonylphenoloxyethylene 10 mol OE (NFOE)  1200 g
     Water  5000 g
     1N HCl (after 60 min stirring) adjust pH 2.8 - 3.0  ~ 160 g
    Example 4. Procedure for obtaining a skin based hygrometric sensor.
    The procedure was carried out in the same manner as in Example 1, using 0.4 mm thick animal skin as a 10% hexadecylpyridinium chloride (CHP) ionic surfactant. The system was adjusted to pH 11.8-12.0 with a 1N NaOH solution.
    TABLE 3
     Component  mass
     0.4 mm thick sheep skin  100g
     10% Hexadecylpyridinium Chloride (CHP)  160 g
     10% Nonylphenoloxyethylene 10 mol OE (NFOE)  1200 g
     Water  5000 g
     1N NaOH (after 60 min stirring) adjust pH 11.8 - 12.0  ~ 180 g
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    Sorption / desorption moisture curves showing the mass variation of dry samples in% as a function of relative humidity (0 to 100% RH) are presented in Figure 1. The lower curve corresponds to the sorption curve which shows the evolution of the sample mass by varying the relative humidity from 0 to 100% RH (or water activity (aw) from 0 to 1). To complete the cycle, the desorption curve is also presented in the upper part, which shows the decrease in the mass of the sample by decreasing the relative humidity RH from 100% to 0%.
    From the adsorption / desorption graph for each material, the table of mass / relative humidity equivalences that allows the use of the collagen sheet or the calibrated skin as a moisture sensor was determined.
    The determination of the function that relates the variation of mass expressed in% on dry mass of the sensor as a function of relative humidity is obtained by adjusting the GAB model to the experimental values obtained by using atmospheres with different humidity levels obtained in containers closed using supersaturated solutions of different salts, or by registering the variation of mass using a water vapor desorption / desorption balance from 0 to 100% relative humidity. The function that relates the mass of the sensor X expressed in% on dry mass with the relative humidity expressed as water activity aw according to the GAB model is as follows:
    X = XmCKaw / [(1-Kaw) (1-Kaw + CKaw)]
    The procedure for obtaining the parameters Xm, C and K of the sensor are explained in the reference (A M Manich et al., J Am Leather Chem Assoc, 105, 229-241, 2010).
    Once the values of the parameters of the model are known, the transformation function is available that allows the tables of equivalence between mass and relative humidity to be prepared, or the function for continuous humidity registration based on the mass of the sensor.
    Table 4 shows the equivalence between mass and relative humidity for the sheet of the combination 3 example in Table 1.
    TABLE 4
     RH (%)  mg HR (%) mg HR (%) mg HR (%) mg
     0  1273.1 26 1323.4 52 1370.6 78 1480.2
     one  1276.0 27 1324.9 53 1373.0 79 1488.3
     2  1278.8 28 1326.5 54 1375.5 80 1497.0
     3  1281.4 29 1328.0 55 1378.0 81 1506.3
     4  1283.9 30 1329.6 56 1380.7 82 1516.3
     5  1286.3 31 1331.2 57 1383.4 83 1527.2
     6  1288.6 32 1332.8 58 1386.3 84 1539.0
     7  1290.7 33 1334.4 59 1389.2 85 1551.9
     8  1292.8 34 1336.0 60 1392.2 86 1566.0
     9  1294.9 35 1337.6 61 1395.4 87 1581.6
     10  1296.8 36 1339.3 62 1398.7 88 1598.7
     eleven  1298.7 37 1341.0 63 1402.2 89 1617.8
     12  1300.5 38 1342.7 64 1405.7 90 1639.0
     13  1302.3 39 1344.4 65 1409.5 91 1663.0
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     14  1304.1 40 1346.2 66 1413.4 92 1690.2
     fifteen  1305.8 41 1348.0 67 1417.5 93 1721.3
     16  1307.5 42 1349.8 68 1421.8 94 1757.1
     17  1309.1 43 1351.6 69 1426.3 95 1799.0
     18  1310.8 44 1353.6 70 1431.0 96 1848.6
     19  1312.4 45 1355.5 71 1436.0 97 1908.3
     twenty  1314.0 46 1357.5 72 1441.3 98 1981.3
     twenty-one  1315.6 47 1359.5 73 1446.8 99 2072.9
     22  1317.1 48 1361.6 74 1452.7 100 2191.1
     2. 3  1318.7 49 1363.8 75 1459.0
     24  1320.2 50 1366.0 76 1465.6
     25  1321.8 51 1368.2 77 1472.7
    When the sensor is coupled to a balance, a continuous recording of the variation in the relative humidity of the environment can be made over time by equivalence with the variation in the mass of the sensor, in a given time. Figure 2 shows the actuation capacity as a hygrometer for the combination 3 sensor in Table 1.
    Example 6. Comparative Example
    The results of hysteresis of other systems are illustrated below without undergoing the process of the invention (treatment with surfactants).
    Vaccine skin samples were used, the first 1.2 mm thick chrome tanned, greased and retanned with a mixture of chromium / mimosa / melamine (sample A) and a second 1.6 mm thick chrome tanned with conventional finish (sample B). Skin dust samples were supplied by the British Leather Confederation (BLC, Northampton, UK) that meet the specifications required for samples called "Official Hide Powder1" by the Society of Leather Technologists and Chemists (SLTC). Skin dust samples were prepared by humidifying and air drying (sample C) and, humidifying and drying by lyophilization (sample D).
    Both in the skin sample (A and B) and in the skin powder samples (C and D) without surfactant treatment, the hysteresis phenomenon is evident, which is evidenced by the difference in the mass of the sample in the equilibrium when it is reached in sorption or desorption. These differences introduce a considerable uncertainty factor in the determination of the relative environmental humidity when the calculation depends on the mass of the sample (Figures 4-7).
    In addition, the use of skin dust, represents a serious inconvenience of manipulation and utilization as a gravimetric sensor for humidity control, since the need to be in direct contact with the environment the humidity of which you want to measure, can not avoid situations of loss of mass in handling that may occur and that will invalidate its use.
    权利要求:
    Claims (31)
    [1]
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    1. - Hygrometric sensor comprising:
    a) between 35% and 60% by weight with respect to the total sensor weight of a collagen material selected from collagen and skin lamina;
    b) between 2% and 20% by weight with respect to the total weight of the sensor of at least one ionic surfactant;
    c) between 30% and 60% by weight with respect to the total weight of the sensor of at least one non-ionic surfactant;
    with the proviso that the percentages of the different sensor components are such that the total does not exceed 100%.
    where the ionic surfactant is selected from sulfates and halides of (C6-C30) alkylpyridinium, sulfates and halides of (C6-C30) quaternary alkylammonium, sulfates and halides of (C6-C30) alkylimidazolinium and alkaline and alkaline earth salts of (C6-C30 ) alkylsulfate, (C6-C30) alkylene ether sulfate, (C6-C30) alkylsulphonate, (C6-C30) alkylbenzenesulfonate, (C6-C30)
    alkylcarboxylate, (C6-C30) alkylethercarboxylate and (C6-C30) alkylsarcosinate and any mixture thereof;
    where the non-ionic surfactant is selected from (C6-C30) polyalkoxylated alcohols, (C6-C30) polyalkoxylated alkylphenols, (C6-C30) polyalkoxylated fatty acids, esters of polyalkoxylated fatty acids, (C6-C30) alkanolamides and (C6-C30 ) alkyl polyglucosides and any of their mixtures;
    and where the collagenous material has a thickness between 20 pm and 1000 pm.
    [2]
    2. - The sensor according to the previous claim, comprising:
    a) between 40% and 55% by weight with respect to the total weight of the collagen material sensor;
    b) between 5% and 15% by weight with respect to the total weight of the sensor of at least one ionic surfactant;
    c) between 35% and 55% by weight with respect to the total weight of the sensor of at least one non-ionic surfactant;
    with the proviso that the percentages of the different components of the sensor are such that the total does not exceed 100%.
    [3]
    3. - The sensor according to any of the preceding claims, wherein the collagenic material has a thickness between 50 pm and 500 pm.
    [4]
    4. - The sensor according to any of the preceding claims, wherein the non-ionic surfactant is (C8-C12) polyoxyethylene alkylphenol, a mixture C9, C10, C11 alkyl polyglucopyranoside with polymerization degree 1.3 or any of its mixtures.
    [5]
    5. - The sensor according to the previous claim, wherein the non-ionic surfactant is nonylphenolpolyoxyethylene.
    [6]
    6. - The sensor according to any of the preceding claims, wherein the ionic surfactant is a cationic surfactant selected from sulfates and halides of (C6-C30) alkylpyridinium sulfates and halides of (C6-C30) quaternary alkylammonium, sulfates and halides of ( C6-C30) alkylimidazolinium and any of its mixtures.
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    [7]
    7. - The sensor according to the preceding claim, wherein the cationic surfactant is selected from (C10-C20) alkylpyridinium halide and (C10-C20) alkylammonium halide and any of its mixtures.
    [8]
    8. - The sensor according to any one of claims 1 to 5, wherein the ionic surfactant is an anionic surfactant selected from alkaline and alkaline earth salts of (C6-C30) alkylsulfate, (C6-C30) alkylether sulfate, (C6-C30) alkylsulfonate, (C6-C30) alkylbenzenesulfonate, (C6-C30) alkylcarboxylate, (C6-C30) alkylethercarboxylate, (C6-C30) alkylsarcosinate and any mixture thereof.
    [9]
    9. - The sensor according to the preceding claim, wherein the anionic surfactant is selected from alkaline or alkaline earth salts of (C10-C16) alkylsulfate, (C10-C16) alkylsulfonate, (C10-C16) alkylbenzenesulfonate and any of their mixtures.
    [10]
    10. - The sensor according to any of the preceding claims, wherein the collagenic material is collagen lamina.
    [11]
    11. - The sensor according to the previous claim where the collagenic material has a thickness of 20 ^ m to 500 ^ m.
    [12]
    12. - The sensor according to any of claims 1 to 9, wherein the collagenic material is skin.
    [13]
    13. - The sensor according to the previous claim where the collagenic material is 200 ^ m to 700 ^ m thick.
    [14]
    14. - Procedure for obtaining a hygrometric sensor according to claims 1 to 13 comprising the following steps:
    a) put in contact in water:
    i) 1 part by weight of a collagen material selected from collagen and skin lamina;
    ii) 0.05 to 0.25 parts by weight of at least one ionic surfactant for each part by weight of the collagenic material;
    iii) 0.7 to 1.8 parts by weight of at least one non-ionic surfactant for each part by weight of the collagenic material;
    b) stir between 0.5 and 24 hours;
    c) drying the collagenous material;
    where the ionic surfactant is selected from sulfates and halides of (C6-C30) alkylpyridinium, sulfates and halides of (C6-C30) quaternary alkylammonium, sulfates and halides of (C6-C30) alkylimidazolinium and alkaline and alkaline earth salts of (C6-C30 ) alkylsulfate, (C6-C30) alkylene ether sulfate, (C6-C30) alkylsulphonate, (C6-C30) alkylbenzenesulfonate, (C6-C30)
    alkylcarboxylate, (C6-C30) alkylethercarboxylate and (C6-C30) alkylsarcosinate and any mixture thereof;
    where the non-ionic surfactant is selected from (C6-C30) polyalkoxylated alcohols, (C6-C30) polyalkoxylated alkylphenols, (C6-C30) polyalkoxylated fatty acids, esters of polyalkoxylated fatty acids, (C6-C30) alkanolamides and (C6-C30 ) alkyl polyglucosides and any of their mixtures;
    and where the collagenic material has a thickness between 20 qm and 1000 qm.
    [15]
    15. - Procedure according to the previous claim, where in step (a) they contact:
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    i) 1 part by weight of a collagen material selected from collagen and skin lamina;
    ii) 0.125 to 0.175 parts by weight of at least one ionic surfactant for each part by weight of the collagenic material;
    iii) 1 to 1.5 parts by weight of at least one non-ionic surfactant for each part by weight of the collagenic material.
    [16]
    16. - Method according to any of claims 14 or 15 wherein the thickness of the collagenic material is 50 pm and 500 pm.
    [17]
    17. - Method according to any of claims 14 to 16, wherein the nonionic surfactant is (C8-C12) polyoxyethylene alkylphenol, a mixture C9, C10, C11 alkyl polyglucopyranoside with polymerization degree 1.3 or any of its mixtures.
    [18]
    18. - Method according to the previous claim, wherein the nonionic surfactant is nonylphenolpolyoxyethylene.
    [19]
    19. - Method according to any of claims 14 to 18, wherein the ionic surfactant is a cationic surfactant selected from sulfates and halides of (C6-C30) alkylpyridinium, sulfates and halides of (C6-C30) quaternary alkylammonium, sulfates and halides of (C6-C30) alkylimidazolinium and any of its mixtures
    [20]
    20. - Method according to the preceding claim, wherein the cationic surfactant is selected from (C10-C20) alkylpyridinium halide and (C10-C20) alkylammonium halide and any of its mixtures.
    [21]
    21. - Method according to any of claims 19 or 20, wherein the pH of step (a) is adjusted between 9 and 13.
    [22]
    22. - Method according to any one of claims 14 to 18 wherein the ionic surfactant is an anionic surfactant selected from alkaline and alkaline earth salts of (C6-C30) alkylsulfate, (C6-C30) alkylether sulfate, (C6-C30) alkylsulfonate, (C6- C30) alkylbenzenesulfonate, (C6-C30) alkylcarboxylate, (C6-C30) alkylethercarboxylate, (C6-C30) alkylsarcosinate and any mixture thereof.
    [23]
    23. - Method according to the preceding claim, wherein the anionic surfactant is selected from alkaline or alkaline earth salts of (C10-C16) alkylsulfate, (C10-C16) alkylsulfonate, (C10-C16) alkylbenzenesulfonate and any of their mixtures.
    [24]
    24. - Method according to any of claims 22 or 23, wherein the pH of step (a) is adjusted between 1 and 4.
    [25]
    25. - Method according to any of claims 14 to 24, wherein the collagenic material is collagen sheet.
    [26]
    26. - Procedure according to the previous claim where the collagenic material has a thickness of 20 pm to 500 pm.
    [27]
    27. - Method according to any of claims 14 to 23, wherein the collagenous material is skin.
    [28]
    28. - Procedure according to the previous claim where the collagenic material has a thickness of 200 pm to 700 pm.
    [29]
    29. - Method according to any of claims 14 to 28, wherein the stirring of step (b) is carried out between 1 and 10 hours.
    [30]
    30. - Method according to any of claims 14 to 29, wherein the drying of step 5 (c) is carried out by lyophilization.
    [31]
    31. - Use of the sensor any of claims 1 to 13 in a gravimetric hygrometer.
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    ES2558846B1|2016-11-22|
    WO2016005630A1|2016-01-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    SU1767459A1|1990-08-20|1992-10-07|Центральная Аэрологическая Обсерватория Госкомгидромета|Method for calibrating humidity sensors based on animal film|CN108507898B|2018-06-11|2021-02-05|中国神华能源股份有限公司|Method for measuring component proportion of ammonium nitrate fuel oil explosive by using saturated oil absorption rate of raw material|
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