CN1206306C - Corrosion inhibiting heat exchange fluid for magnetic refrigerating under ambient temperature - Google Patents
Corrosion inhibiting heat exchange fluid for magnetic refrigerating under ambient temperature Download PDFInfo
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- CN1206306C CN1206306C CN 03127022 CN03127022A CN1206306C CN 1206306 C CN1206306 C CN 1206306C CN 03127022 CN03127022 CN 03127022 CN 03127022 A CN03127022 A CN 03127022A CN 1206306 C CN1206306 C CN 1206306C
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- heat exchange
- exchange fluid
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- inhibiting heat
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Abstract
The present invention provides a corrosion inhibiting heat exchange fluid for magnetic refrigeration at room temperature, which comprises distilled water, an antifreezing agent, inorganic matter comprising monovalent cations and OH radicals, and one kind of benzotriazole (BTA), a triazole (BTA) derivative, 2-mercaptobenzoxazole (MBO) and a 2-mercaptobenzoxazole (MBO) derivative whose content is from 0.1 to 4 wt%. The pH value of the corrosion inhibiting heat exchange fluid is between 6.5 and 12, and the optimization range of the pH value is between 8 and 10. The inorganic matter comprising the monovalent cations and the OH radicals is NaOH or KOH. The antifreezing agent is ethanol or ethylene glycol, and the content of the antifreezing agent is from 0 to 30 % by volume. The corrosion inhibiting heat exchange fluid can be regulated according to a refrigeration temperature range required by a magnetic refrigeration machine. The corrosion inhibiting heat exchange fluid has the advantages that the corrosion inhibiting heat exchange fluid can be used for greatly delaying the corrosion action of heat exchange fluid to Gd and Gd alloy.
Description
Technical field
The invention belongs to the room temperature magnetic refrigerating technical field, a kind of room temperature magnetic refrigerating rust inhibition heat exchange fluid particularly is provided, can slow down the magnetic refrigeration working substance corrosion.
Background technology
The room temperature magnetic refrigerating technology is to utilize in the magneticsubstance magnetic moment to carry out in externally-applied magnetic field in order and big magnetic entropy takes place during disorder transformation to change and realize freezing.In the magnetic Refrigeration Technique, what use is solid magnetic refrigeration working medium and externally-applied magnetic field, therefore it does not use the obnoxious flavoures such as fluorine Lyons that present traditional Gas Refrigerator uses, to environment without any pollution, in addition according to Theoretical Calculation, its efficient is far above present gas refrigeration, so it has huge potential application market.
Around the room temperature magnetic refrigerating technology, a lot of patents have been arranged.The patent of the magnetic refrigeration working substance of the relevant great magnetic entropy variationization of for example having authorized has US5743095, ZL93100231.1 etc., and patent US4727722, US5934078 etc. provide the concrete device of realizing the room temperature magnetic refrigerating technology.For example at US4727722 (related data: Adv.Cry.Eng., 1987 (33): 757) magnetic refrigerator in the patent is a rotary structure, adopted pumping backflow heat exchange mode, the magnetic refrigeration cycle is similar to the Ericsson circulation, magnetic refrigeration working substance is that thick 76 μ m, intermediate space 127 μ m are so that the metal gadolinium Gd stack of laminations of fluid flow, heat exchange medium is a water, and under the 0.9T changes of magnetic field, 270g Metal Gd sheet has obtained the temperature of 11K and striden.US5934078 (related data: Adv.Cry.Eng., 1998 (43): 1759) the magnetic refrigerator mode of operation of patent is reciprocating type, refrigeration working medium is spherical metal gadolinium Gd, with water (adding frostproofer) as heat exchange fluid.Model machine peak power under 5T, 1.5T externally-applied magnetic field Strength Changes with the US5934078 patent is respectively 600W, 150W, and maximum temperature is striden and is respectively 38K, 16K.
In sum, current room temperature magnetic Refrigeration Technique generally all selects Gd, Gd alloy or rare earth compound as magnetic refrigeration working substance, because find in the research of numerous materials at present, has only Gd, Gd alloy and rare earth compound to have big adiabatic demagnetization effect.In room temperature magnetic refrigerating, all adopted water as heat exchange fluid in addition.But when using Gd, Gd alloy, if, there be the etching problem of water to Gd, Gd alloy as heat exchange medium in water as magnetic refrigeration working substance.During as heat exchange medium, it will have obvious corrosion to Gd, Gd alloy in 24 hours with distilled water, and as heat exchange medium, within several hrs, it just has obvious corrosion to Gd, Gd alloy with general tap water.
Summary of the invention
The object of the present invention is to provide a kind of room temperature magnetic refrigerating rust inhibition heat exchange fluid, this fluid can prolong the life-span of magnetic refrigeration working substance.Solution prolongs the life-span of Gd, Gd alloy to Gd, Gd alloy corrosion.
Gd is corroded in general tap water very soon, and the surface generates white cotton-shaped corrosion product; In distilled water, because impurity seldom, can see that Gd slowly corrodes, the surface is the cotton-shaped corrosion product of adularescent also.The polarization curve of Gd in tap water and distilled water represented as Fig. 1.
Fluidic of the present invention is formed and is comprised: distilled water, frostproofer, a kind of in the benzotriazole (BTA) of the 0.1-4 weight % that inorganics that monovalent cation and OH root are formed and content are the fluid gross weight, benzotriazole (BTA) derivative, 2-mercaptobenzoxazole (MBO), four kinds of materials of 2-mercaptobenzoxazole (MBO) derivative; The pH value of this rust inhibition heat exchange fluid is between 6.5～12, and the optimum range of pH value is between 8～10.Frostproofer is ethanol or ethylene glycol, and frostproofer content is 0-30 volume %, regulates according to the magnetic refrigerator operating temperature range.
Contain in the rust inhibition heat exchange fluid of the present invention trace in water, can not generate sedimentary, can provide 1 valency cationic, contain OH
-1Inorganics, NaOH for example, KOH etc., to change the pH value of water, make the pH value of water in neutrality in the weakly alkaline scope.Under this environment, tangible passivation takes place in Gd and Gd alloy surface, has effectively protected it no longer to be corroded.
According to patent and bibliographical informations such as US4727722, US5934078, in the room temperature magnetic refrigerating technology, generally all consider to adopt water to add deicing fluid as heat exchange fluid, because the thermal capacitance of water is big, and good flowability is arranged.Impurity is to the corrosion of Gd or rare earth compound in the water in order to reduce again, and the present invention adopts distilled water as base fluid.The content of the base fluid distilled water of rust inhibition heat exchange fluid of the present invention and the summation of deicing fluid reaches more than the 96wt%, makes heat exchange fluid of the present invention still have big thermal capacitance and good flowability.
The derivative that contains benzotriazole (BTA), benzotriazole (BTA) derivative, 2-mercaptobenzoxazole (MBO), 2-mercaptobenzoxazole (MBO) in the rust inhibition heat exchange fluid of the present invention.These materials add and help generating fine and close passive film at Gd and Gd alloy surface, have stoped the corrosion of Gd and Gd alloy.And benzotriazole (BTA), 2-mercaptobenzoxazole materials such as (MBO) also have retarding action to the corrosion of copper.Therefore rust inhibition heat exchange fluid of the present invention has not only prevented the corrosion of Gd and Gd alloy, has also effectively prevented the corrosion as the copper tube of circulation duct.The content of the derivative of benzotriazole (BTA), triazole (BTA) derivative, 2-mercaptobenzoxazole (MBO), 2-mercaptobenzoxazole (MBO) with greater than 0.1g for well, otherwise this material does not delay corrosive nature to Gd and Gd alloy.
The present invention specifically prepares being operating as of rust inhibition heat exchange fluid: in base fluid, add earlier materials such as Weibull, BTA, add the inorganics that has the OH root again after making solution evenly, the content of the inorganics of adding with regulate pH value below 12 for well.Preferable range 8～12, best pH value is 9 to 10.In addition, all add base fluids material total content with guarantee base fluid and deicing fluid summation at 96wt% for well.Also can add the inorganics that has the OH root earlier, make the solution meta-alkalescence, make the evenly derivative of back adding benzotriazole (BTA), triazole (BTA) derivative, 2-mercaptobenzoxazole (MBO), 2-mercaptobenzoxazole (MBO) of solution, regulate pH value.
The invention has the advantages that: can delay the corrosive nature of heat exchange fluid to Gd and Gd alloy significantly, use rust inhibition heat exchange fluid of the present invention, all can not measure Gd and Gd alloy because of the weightless effect of corrosive about 240h, the surface is light always.And single within 24h, just can obviously find out the corrosion of Gd and Gd alloy, surperficial adularescent floss generation with the heat exchange fluid of distilled water.In addition, because 96wt% is that distilled water and deicing fluid are formed in the base fluid, therefore heat exchange fluid of the present invention does not influence the heat exchange of magnetic refrigeration working substance.
Description of drawings
Fig. 1 is the polarization curve of Metal Gd in tap water and distilled water.X-coordinate is the logarithmic value of corrosion current, and ordinate zou is a corrosion potential.
Fig. 2 is the polarization curve of metal gadolinium in the rust inhibition heat exchange fluid.X-coordinate is the logarithmic value of corrosion current, and ordinate zou is a corrosion potential.
Embodiment
Sample is prepared: will approach garden sheet sample surfaces and polish to 800 orders with abrasive paper for metallograph, and use the acetone clean surface, and make its drying then.
The contrast experiment
After making lacing film soak 72 hours in tap water with metal gadolinium sample, rate of weight loss is 1.542g/ (m
2H); Soak after 64 hours in distilled water, rate of weight loss is 0.918g/ (m
2H).The polarization curve of tap water and distilled water such as Fig. 1
Base fluid is a distilled water, and the pH value is 9,10,12 rust inhibition heat exchange fluid, the metal gadolinium is made lacing film be immersed in wherein, respectively through 376,375, observes after 731 hours, and the specimen surface light is not measured changes in weight with weight-loss method.The polarization curve of this rust inhibition heat exchange fluid such as Fig. 2.
Embodiment 2
Base fluid is a distilled water, is 1.5% Weibull with weight percent, adds the rust inhibition heat exchange fluid that NaOH regulates pH value to 6.8, and the metal gadolinium soaked 360 hours after making lacing film, produced a small amount of spot corrosion.Rate of weight loss is 0.028g/ (m
2H).Make lacing film with red copper, observe after soaking in 200 hours, light as new is not measured changes in weight with weight-loss method.
Base fluid is a distilled water, and the weight percent of benzotriazole (BTA) is respectively 1%, 2.5% rust inhibition heat exchange fluid, and metal gadolinium lacing film soaked after 200,372 hours to be observed, and metal gadolinium lacing film surface-brightening does not have the obvious corrosion product.Make lacing film with red copper simultaneously, observe after soaking in 158 hours, red copper system lacing film surface-brightening is not measured changes in weight with weight-loss method.
Embodiment 4
Base fluid is a distilled water, and adding NaOH, to make the pH value of solution be 12, adds BTA again, and making the pH value is 7 rust inhibition heat exchange fluid, and metal gadolinium lacing film soaks observation after 370 hours therein, and surface-brightening is not measured changes in weight with weight-loss method.
Claims (2)
1, a kind of room temperature magnetic refrigerating rust inhibition heat exchange fluid. it is characterized in that: this fluidic is formed and is comprised: distilled water, frostproofer, NaOH that monovalent cation and OH root are formed or KOH and content are a kind of in the benzotriazole, benzotriazole derivative, 2-mercaptobenzoxazole, four kinds of materials of 2-mercaptobenzoxazole derivative of the 0.1-4 weight % of fluid gross weight, the pH value of this rust inhibition heat exchange fluid is between 6.5～12, and frostproofer content is 0～30 volume %.
2, the described room temperature magnetic refrigerating of claim 1 rust inhibition heat exchange fluid is characterized in that: frostproofer is ethanol or ethylene glycol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03127022 CN1206306C (en) | 2003-05-23 | 2003-05-23 | Corrosion inhibiting heat exchange fluid for magnetic refrigerating under ambient temperature |
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| CN 03127022 CN1206306C (en) | 2003-05-23 | 2003-05-23 | Corrosion inhibiting heat exchange fluid for magnetic refrigerating under ambient temperature |
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| CN1456633A CN1456633A (en) | 2003-11-19 |
| CN1206306C true CN1206306C (en) | 2005-06-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101514458B (en) * | 2007-11-27 | 2011-04-20 | 北京科技大学 | Inhibitor in aqueous heat exchange medium for La-Fe-Si series room temperature magnetic refrigeration materials |
| CN103030240A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Circulating water treatment method adopting deionized water as supplement water |
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