CN109518056A - A kind of environment-friendly type liquid state alloy, preparation method and mercury-free glass thermometer - Google Patents
A kind of environment-friendly type liquid state alloy, preparation method and mercury-free glass thermometer Download PDFInfo
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- CN109518056A CN109518056A CN201811395955.6A CN201811395955A CN109518056A CN 109518056 A CN109518056 A CN 109518056A CN 201811395955 A CN201811395955 A CN 201811395955A CN 109518056 A CN109518056 A CN 109518056A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K5/00—Measuring temperature based on the expansion or contraction of a material
- G01K5/02—Measuring temperature based on the expansion or contraction of a material the material being a liquid
- G01K5/04—Details
- G01K5/12—Selection of liquid compositions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K5/00—Measuring temperature based on the expansion or contraction of a material
- G01K5/02—Measuring temperature based on the expansion or contraction of a material the material being a liquid
- G01K5/22—Measuring temperature based on the expansion or contraction of a material the material being a liquid with provision for expansion indicating over not more than a few degrees
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Abstract
The present invention relates to a kind of environment-friendly type liquid state alloy, preparation method and mercury-free glass thermometers.Environment-friendly type liquid state alloy provided by the invention, the component with following weight proportion: 62 ~ 78wt% of gallium, 10 ~ 24wt% of indium, 6 ~ 14.5wt% of tin, 0.05 ~ 1wt% of bismuth, 0.1 ~ 0.8wt% of antimony, silver 0.005 ~ 0.5wt%, 0.02 ~ 1.2wt% of zinc, 0.01 ~ 0.5wt% of copper.Environment-friendly type of the invention is free of the liquid alloy and preparation method thereof of mercury metal, it is mainly adjusted by alloying element composition, preparation process, the liquid alloy that freezing point is low, stability is good is prepared, traditional mercury clinical thermometer can be replaced using this alloy as the temperature sensing liquid of glass thermometer.
Description
Technical field
The present invention relates to a kind of environment-friendly type liquid state alloy, preparation method and glass thermometer, the freezing point of the alloy is low, steady
Qualitative good, gained alloy graining point can be down to -35 DEG C, and liquid alloy of the invention is on medical instrument, the fields such as consumer electronics
Suffer from good application.
Background technique
Common thermometer is used to detect the temperature at the positions such as human oral cavity, oxter, and working solution is usually mercury, is stored in
In the glass envelope of bottom end, vacuole volume is much larger than the volume in capillary, and under the variation of temperature, the volume of mercury occurs in vacuole
Faint linear expansion reflects surveyed temperature by the length of fluid column in capillary.
Clinical thermometer has been born upper a century, although its structure size is constantly changing with the time, in vacuole
What temperature sensing liquid used is always mercury, and mercury is a kind of extremely toxic substance, and since Japanese minamata disease, people gradually recognize water
The harm of silver starts the use of conscious limitation mercury.China also endorsed " Minamata pact " in 2016, and will be in 2020
Year starts to forbid producing and export mercurous product.
Before more than ten years, occur it is a kind of with gallium indium tin be main component novel liquid alloy, the alloy earliest by
The Geratherm company exploitation of Germany, is applied to glass thermometer and replaces original mercury, and achieve good effect
Fruit.In recent years, domestic many scholars breached technical barrier, started the liquid alloy expansion research to the system, from formula
The application of alloy is studied, many breakthrough research achievements are also achieved.
Patent 200610024617.2 provides a kind of gallium indium tin sodium-potassium-lithium alloy that stable liquid is able to maintain at 5 ~ 42 DEG C,
The alloy can be used for the temperature sensing liquid of mercury-free glass thermometer, but sodium-potassium-lithium is all active metal, meets water energy and directly reacts, has
Certain risk, and have higher difficulty in preservation and production process.
Patent 201710186902.2 provides a kind of liquid alloy of alternative mercury, by its weight percent: gallium 55 ~
65%, indium 16 ~ 22%, tin 10 ~ 15%, lead 2 ~ 5% and thallium 1 ~ 3%.But the lead and thallium in its ingredient all have stronger toxicity, and thallium is more
It is to have severe toxicity, which has certain risk, and promoting in production process and later period all has certain difficulty.
Summary of the invention
The main object of the present invention is to provide a kind of liquid alloy and preparation method thereof of the environment-friendly type without mercury metal,
It is mainly adjusted by alloying element composition, preparation process, the liquid alloy that freezing point is low, stability is good is prepared, is closed with this
Gold can replace traditional mercury clinical thermometer as the temperature sensing liquid of glass thermometer.
In order to complete above-mentioned purpose, the present invention provides a kind of environment-friendly type liquid state alloys, with following weight proportion
Component: 62 ~ 78wt% of gallium, 10 ~ 24wt% of indium, 6 ~ 14.5wt% of tin, 0.05 ~ 1wt% of bismuth, 0.1 ~ 0.8wt% of antimony, silver 0.005 ~
0.5wt%, 0.02 ~ 1.2wt% of zinc, 0.01 ~ 0.5wt% of copper.
One Preferable scheme is that, environment-friendly type liquid state alloy have following weight proportion component: 65 ~ 74wt% of gallium, indium
12.5 ~ 22wt%, 6 ~ 13.5wt% of tin, 0.1 ~ 0.55wt% of bismuth, 0.2 ~ 0.6wt% of antimony, silver 0.01 ~ 0.3wt%, 0.05 ~ 1wt% of zinc,
0.02 ~ 0.2wt% of copper.
One Preferable scheme is that, the liquid alloy is in -35 ~ 1900 DEG C of holding liquid.
The manufacturing method of environment-friendly type liquid state alloy provided by the invention comprising step below:
S1: gallium, indium, tin, bismuth, antimony, silver, zinc, copper are weighed；
S2: raw material load weighted in S1 step is put into vacuum melting furnace, carries out vacuum pumping；
S3: after vacuum degree reaches requirement, heat up melting, and smelting temperature is controlled at 500 ~ 1000 DEG C,
S4: held for some time is filled with argon gas or nitrogen, carries out natural cooling to alloy, takes out after being cooled to room temperature；
S5: alkali cleaning stirring is carried out to alloy with the NaOH solution of 2 ~ 4mol/L concentration, oxide on surface is removed, obtains environment-friendly type liquid
State alloy, wherein component of the environment-friendly type liquid state alloy with following weight proportion: 62 ~ 78wt% of gallium, 10 ~ 24wt% of indium, tin 6 ~
14.5wt%, 0.05 ~ 1wt% of bismuth, 0.1 ~ 0.8wt% of antimony, silver 0.005 ~ 0.5wt%, 0.02 ~ 1.2wt% of zinc, 0.01 ~ 0.5wt% of copper.
One Preferable scheme is that, environment-friendly type liquid state alloy have following weight proportion component: 65 ~ 74wt% of gallium, indium
12.5 ~ 22wt%, 6 ~ 13.5wt% of tin, 0.1 ~ 0.55wt% of bismuth, 0.2 ~ 0.6wt% of antimony, silver 0.01 ~ 0.3wt%, 0.05 ~ 1wt% of zinc,
0.02 ~ 0.2wt% of copper.
One Preferable scheme is that, in the S1, the purity of each raw metal is 99.9% or more；Described
In S2, material is put into silica crucible, silica crucible is put into vacuum melting furnace；In S3, vacuum degree reaches 1 ×
10-3Pa or less starts to warm up melting；In S5, obtained liquid alloy is in -35 ~ 1900 DEG C of holding liquid.
A kind of mercury-free glass thermometer provided by the invention, mercury-free glass thermometer has bulb, in the bulb,
It is interior to be filled with environment-friendly type liquid state alloy, component of the environment-friendly type liquid state alloy with following weight proportion: 62 ~ 78wt% of gallium, indium 10 ~
24wt%, 6 ~ 14.5wt% of tin, 0.05 ~ 1wt% of bismuth, 0.1 ~ 0.8wt% of antimony, silver 0.005 ~ 0.5wt%, 0.02 ~ 1.2wt% of zinc, copper
0.01~0.5wt%。
One Preferable scheme is that, environment-friendly type liquid state alloy have following weight proportion component: 65 ~ 74wt% of gallium, indium
12.5 ~ 22wt%, 6 ~ 13.5wt% of tin, 0.1 ~ 0.55wt% of bismuth, 0.2 ~ 0.6wt% of antimony, silver 0.01 ~ 0.3wt%, 0.05 ~ 1wt% of zinc,
0.02 ~ 0.2wt% of copper.
One Preferable scheme is that, pressure in capillary is 4 × 10-5~5×10-4Pa；The liquid alloy -35 ~
1900 DEG C of holding liquid.
The technical advantage of liquid alloy preparation process of the invention are as follows: it is provided by the invention based on gallium, indium, tin, bismuth,
Antimony, silver, zinc be auxiliary element liquid alloy it is nontoxic and not volatile, have the characteristics that it is environmental-friendly, wherein being added
Bismuth the mobility of liquid alloy can be improved, the oxidation resistance of liquid alloy can be improved in antimony, and silver, zinc, copper help to improve liquid
The stability of state alloy.Using the technique of high-temperature vacuum melting, help to prevent alloy oxidation, the inertia that when natural cooling is filled with
Gas can protect alloy, and can accelerate the cooling velocity of alloy, which is conducive to each element in alloy and mixes
Uniformly.NaOH solution alkali cleaning used can remove oxide in alloy when purification, be conducive to improve mercury-free glass thermometer
Qualification rate.
A kind of mercury-free glass thermometer provided by the invention wherein closes in bulb, full of the liquid prepared through above-mentioned technique
Gold, the pressure in capillary are 4 × 10-5~5×10-4Pa, resulting mercury-free glass thermometer measurement is accurate, asepsis environment-protecting,
Under the worldwide trend for prohibiting mercury, there is good prospect.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the structural schematic diagram of mercury-free glass thermometer embodiment of the invention.
Description of symbols
1, mercury-free glass thermometer, 2, bulb,.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description.In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Embodiment 1
The proportion of the environment-friendly type liquid state alloy of the present embodiment is as follows: gallium 66.2%, indium 19.5%, tin 12.1%, bismuth 0.35%, antimony
0.51%, silver 0.2%, zinc 1%, copper 0.14%.Claim to prepare raw material metal according to the above ratio, be put into vacuum melting furnace and vacuumize,
To vacuum degree to 8 × 10-4Pa starts melting, and smelting temperature is 660 DEG C, and cooled to room temperature is taken out after melting, uses
The NaOH solution of 2mol/L cleans liquid alloy, removes oxide after being sufficiently stirred.It is prepared using above-mentioned liquid alloy
Mercury-free glass thermometer out fills above-mentioned liquid as shown in Figure 1, mercury-free glass thermometer 1 has bulb, 2 in bulb, 2
Alloy, wherein the pressure in capillary is 3.7 × 10-4Pa。
Embodiment 2
The proportion of the environment-friendly type liquid state alloy of the present embodiment is as follows: gallium 69.8%, indium 17.4%, tin 10.8%, bismuth 0.45%, antimony
0.42%, silver 0.18%, zinc 0.87%, copper 0.08%.Claim to prepare raw material metal according to the above ratio, is put into vacuum melting furnace and takes out very
Sky, to vacuum degree to 8.5 × 10-4Pa starts melting, and smelting temperature is 695 DEG C, and cooled to room temperature is taken out after melting,
Liquid alloy is cleaned with the NaOH solution of 2mol/L, removes oxide after being sufficiently stirred.Use above-mentioned liquid alloy system
For mercury-free glass thermometer out, the pressure in capillary is 3.2 × 10-4Pa。
Embodiment 3
The proportion of the environment-friendly type liquid state alloy of the present embodiment is as follows: gallium 72.2%, indium 17.2%, tin 8.5%, bismuth 0.42%, antimony
0.58%, silver 0.14%, zinc 0.90%, copper 0.06%.Claim to prepare raw material metal according to the above ratio, is put into vacuum melting furnace and takes out very
Sky, to vacuum degree to 6.9 × 10-4Pa starts melting, and smelting temperature is 735 DEG C, and cooled to room temperature is taken out after melting,
Liquid alloy is cleaned with the NaOH solution of 2.5mol/L, removes oxide after being sufficiently stirred.Use above-mentioned liquid alloy
Mercury-free glass thermometer is prepared, the pressure in capillary is 6.4 × 10-5Pa。
Embodiment 4
The proportion of the environment-friendly type liquid state alloy of the present embodiment is as follows: gallium 73.5%, indium 17.8%, tin 7.1%, bismuth 0.23%, antimony
0.36%, silver 0.10%, zinc 0.75%, copper 0.16%.Claim to prepare raw material metal according to the above ratio, is put into vacuum melting furnace and takes out very
Sky, to vacuum degree to 7.3 × 10-4Pa starts melting, and smelting temperature is 720 DEG C, and cooled to room temperature is taken out after melting,
Liquid alloy is cleaned with the NaOH solution of 3mol/L, removes oxide after being sufficiently stirred.Use above-mentioned liquid alloy system
For mercury-free glass thermometer out, the pressure in capillary is 8.2 × 10-5Pa。
Obviously, described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of environment-friendly type liquid state alloy, which is characterized in that the component including following weight proportion:
62 ~ 78wt% of gallium, 10 ~ 24wt% of indium, 6 ~ 14.5wt% of tin, 0.05 ~ 1wt% of bismuth, 0.1 ~ 0.8wt% of antimony, silver 0.005 ~
0.5wt%, 0.02 ~ 1.2wt% of zinc, 0.01 ~ 0.5wt% of copper.
2. environment-friendly type liquid state alloy according to claim 1, which is characterized in that the environment-friendly type liquid state alloy includes as follows
The component of weight proportion: 65 ~ 74wt% of gallium, 12.5 ~ 22wt% of indium, 6 ~ 13.5wt% of tin, 0.1 ~ 0.55wt% of bismuth, antimony 0.2 ~
0.6wt%, silver 0.01 ~ 0.3wt%, 0.05 ~ 1wt% of zinc, 0.02 ~ 0.2wt% of copper.
3. environment-friendly type liquid state alloy according to claim 2, which is characterized in that the liquid alloy is kept at -35 ~ 1900 DEG C
Liquid.
4. a kind of manufacturing method of environment-friendly type liquid state alloy, which is characterized in that include the steps that following:
S1: gallium, indium, tin, bismuth, antimony, silver, zinc, copper are weighed；
S2: raw material load weighted in S1 step is put into vacuum melting furnace, carries out vacuum pumping；
S3: after vacuum degree reaches requirement, heat up melting, and smelting temperature is controlled at 500 ~ 1000 DEG C,
S4: held for some time is filled with argon gas or nitrogen, carries out natural cooling to alloy, takes out after being cooled to room temperature；
S5: alkali cleaning stirring is carried out to alloy with the NaOH solution of 2 ~ 4mol/L concentration, oxide on surface is removed, obtains environment-friendly type liquid
State alloy, wherein environment-friendly type liquid state alloy includes the component of following weight proportion: 62 ~ 78wt% of gallium, 10 ~ 24wt% of indium, tin 6 ~
14.5wt%, 0.05 ~ 1wt% of bismuth, 0.1 ~ 0.8wt% of antimony, silver 0.005 ~ 0.5wt%, 0.02 ~ 1.2wt% of zinc, 0.01 ~ 0.5wt% of copper.
5. the manufacturing method of environment-friendly type liquid state alloy according to claim 4, which is characterized in that environment-friendly type liquid state alloy packet
Include the component of following weight proportion: 65 ~ 74wt% of gallium, 12.5 ~ 22wt% of indium, 6 ~ 13.5wt% of tin, 0.1 ~ 0.55wt% of bismuth, antimony 0.2 ~
0.6wt%, silver 0.01 ~ 0.3wt%, 0.05 ~ 1wt% of zinc, 0.02 ~ 0.2wt% of copper.
6. the manufacturing method of environment-friendly type liquid state alloy according to claim 5, which is characterized in that each in the S1
The purity of kind raw metal is 99.9% or more；In the S2, material is put into silica crucible, silica crucible is put
Enter in vacuum melting furnace；In S3, vacuum degree reaches 1 × 10-3Pa or less starts to warm up melting；In S5, obtained liquid is closed
Gold is in -35 ~ 1900 DEG C of holding liquid.
7. a kind of mercury-free glass thermometer, which is characterized in that mercury-free glass thermometer has bulb, fills out in the bulb,
Filled with environment-friendly type liquid state alloy, the environment-friendly type liquid state alloy includes the component of following weight proportion: 62 ~ 78wt% of gallium, and indium 10 ~
24wt%, 6 ~ 14.5wt% of tin, 0.05 ~ 1wt% of bismuth, 0.1 ~ 0.8wt% of antimony, silver 0.005 ~ 0.5wt%, 0.02 ~ 1.2wt% of zinc, copper
0.01~0.5wt%。
8. mercury-free glass thermometer according to claim 7, which is characterized in that environment-friendly type liquid state alloy includes following weight
The component of proportion: 65 ~ 74wt% of gallium, 12.5 ~ 22wt% of indium, 6 ~ 13.5wt% of tin, 0.1 ~ 0.55wt% of bismuth, 0.2 ~ 0.6wt% of antimony, silver
0.01 ~ 0.3wt%, 0.05 ~ 1wt% of zinc, 0.02 ~ 0.2wt% of copper.
9. according to the mercury-free glass thermometer of claim 7 or 8, which is characterized in that in the capillary of mercury-free glass thermometer
Pressure be 4 × 10-5~5×10-4Pa；The liquid alloy is in -35 ~ 1900 DEG C of holding liquid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111534282A (en) * | 2019-12-16 | 2020-08-14 | 有研工程技术研究院有限公司 | Phase-change heat storage material with low melting point and high volume latent heat, and preparation method and application thereof |
| CN112358854A (en) * | 2020-10-12 | 2021-02-12 | 湖南中材盛特新材料科技有限公司 | Liquid metal heat-conducting paste and preparation method and application thereof |
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Application publication date: 20190326 |