CN107267832A - A kind of porous liquid metal material of temperature control irreversible transition and its preparation and application - Google Patents
A kind of porous liquid metal material of temperature control irreversible transition and its preparation and application Download PDFInfo
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- CN107267832A CN107267832A CN201710442911.3A CN201710442911A CN107267832A CN 107267832 A CN107267832 A CN 107267832A CN 201710442911 A CN201710442911 A CN 201710442911A CN 107267832 A CN107267832 A CN 107267832A
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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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0036—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/02—Surgical adhesives or cements; Adhesives for colostomy devices containing inorganic materials
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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
- C22C1/08—Alloys with open or closed pores
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/06—Flowable or injectable implant compositions
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Abstract
A kind of porous liquid metal material of temperature control irreversible transition, liquid metal internal has loose structure, contain gas in loose structure, normality is liquid, cooling or heating can be changed into solid phase from liquid phase, the solid metallic of high-density high-strength can be turned into after cooling, heating can also be changed into loose porous solid metallic from liquid, liquid condition cannot be changed into by cooling again after heating, it can be changed into solid matter by liquid is permanent by high-temperature process, this material has porosity high, density is small, good conductivity, insulation effect is good, stability is good, the advantages of excellent magnetic, the characteristics of also there is metal material, this high temperature causes liquid-solid-phase changeable to break traditional Transformation Principle, and heating treatment can allow the material of liquid permanent cured, this material combines many excellent properties, in electronics industry, internal robot, magnetic control drives, there is important application in the fields such as metal mending.
Description
Technical field
The invention belongs to porous liquid metal material technical field, more particularly to a kind of porous liquid of temperature control irreversible transition
Metal material and its preparation and application.
Background technology
Traditional normal temperature liquid metal such as mercury, has there is very long applicating history, but its toxicity limits its application, existing
Slowly turn into a star of Material Field as liquid metal in gallium metal and its alloy.It not only has good electric conductivity
Energy and heat conductivility, and also deformability so that liquid metal robot moves towards reality from science fiction, and liquid is reported before
Metal is eaten and can moved past one hour after a small amount of aluminium, and the good morphotropism of liquid metal carries for the preparation of soft robot
Having supplied may.The biocompatibility of liquid metal is good, has been reported that and shows that gallium indium liquid metal can be as the neural life of connection
Thing material.Following liquid metal is also expected to as medicine carrying material implant, but this density of material is higher, while mobility
It is very strong, carry medicine and fixed bit is equipped with certain difficulty.If all difficulty then can be produced again in injection process with solid, so
It is desirable that can prepare can between solid-liquid phase transformation material, when injecting in a liquid state, when reaching specified location,
Then it is changed into solid-state to be fixed.We can cause liquid metal by adding some nontoxic nano materials in liquid metal
With how species specific performance, such as the loose structure with low-density, it can suspend or float in liquid environment.Simultaneously
The thermal insulation become reconciled with high conductivity.The most important, this material can realize the heating irreversible transition of material,
This phenomenon is different from traditional theory.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of temperature control irreversible transition is porous
Liquid metal material and its preparation and application, can solve deficiency of the current liquid metal in biomedicine field, such as fix
Shape is difficult, and density is big, and motion and phase transformation are difficult to control.By adding metallic particles so that with porous low density structures, together
When the characteristics of there is soft material.It can be controlled to move by magnetic field.Whole preparation process is simple to operate, and raw material are easy to get, mistake
Journey controllability is strong, and density can be adjusted.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of porous liquid metal material of temperature control irreversible transition, has loose structure, loose structure in liquid metal internal
In containing the gas such as hydrogen, normality is liquid, and cooling or heating can be changed into solid phase from liquid phase.
Specifically, the fusing point of the porous liquid metal material of temperature control irreversible transition is at 25 degree or so, and low temperature can be protected
Deposit, about start solidification at 60 degree, cooling will not recover liquid condition after solidification.But by adding concentrated hydrochloric acid and stirring
Afterwards, liquid condition can be reverted to.
The liquid metal is gallium base series alloy, such as gallium-indium alloy, gallium tin alloy, gallium-indium-tin alloy, gallium kirsite etc.,
The gas is hydrogen.
The cooling is to be cooled to 15 DEG C of freezing point, the heating refer to be warming up to 50 DEG C and more than, normality refers to room temperature
Normal pressure.Cooling is changed into solid metallic from liquid phase, and heating is changed into solid phase soft metal from liquid phase.
The intensity of the solid phase soft metal is by acid-base value control, when under alkaline environment, intensity increases.
Density reduces after heating, enabling swim in the water surface and ethanol surface.
Under static conditions, elapse over time, after 3-5 hours (time changes with iron content), liquid by
Fade to solid-state.
The preparation method of the porous liquid metal material of temperature control irreversible transition of the present invention, comprises the following steps：
Step 1：In the micro-nano ferrous powder granules of liquid metal surface spreading, hydrochloric acid is added afterwards until being totally submerged liquid gold
Category, stirring causes iron powder to consume completely, and the liquid metal for getting rid of low magnetic is separated by magnetic field, obtains ferromagnetism liquid gold
Category；
Step 2：Redox reaction occurs in hydrochloric acid for ferromagnetism liquid metal, produces a large amount of hydrogen, strong by heating
Magnetic liquid metal makes its expansion form loose structure.
In the step 1, the mass ratio of liquid metal and micro-nano ferrous powder granules is (10:1)~(2；1), Hydrochloric acid adequate amount；
More than the Gauss of magnetic field intensity 50, adsorb and be continuing with ferromagnetism liquid metal, weak magnetic liquid metal return to step 1.
When micro-nano ferrous powder granules mass content is 15% in the material that the step 2 is obtained, performance is optimal, passes through 60 DEG C
Heating can both be changed into the softer metals of porous low-density in ten minutes above.
The porous liquid metal material of temperature control irreversible transition of the present invention, good conductivity, electrical conductivity is about 0.2x107S/
M, excellent heat insulating performance, thermal conductivity is about 0.3W/mK.Porosity is high, and deformability is strong.Can be as soft material in such as software
There is application in many fields such as robot, prepare acceptor of energy, shock absorbing buffer, soda acid sensor and electric sensor.By
Be changed into solid-state process in the heating of its liquid irreversible, liquid injection can enter in normal temperature, then as time passage or
Heating irreversible can be changed into solid-state.This has wide answer in terms of medical domain such as blood vessel blockage, drug delivery
Use prospect.
Compared with prior art, the beneficial effects of the invention are as follows：
Metal lightweight, density is less than 0.5g/ml, and loose structure medicine-carried, thermal insulation electric conductivity is good, elevated cure
It is irreversible, the liquid flowed under normal temperature can be changed into the soft species metal of solid-state by adjusting temperature or time, different
Acid-base property can obtain the porous metals of varying strength.The metal of porous solid can revert to liquid again after adding concentrated hydrochloric acid stirring
State, in the presence of water, can repeat to produce loose structure, after its loose structure is destroyed, and can constantly repeat to produce again
New loose structure.
Brief description of the drawings
Fig. 1 is the irreversible liquid metal preparation figure of temperature control phase transformation.
Fig. 2 is application schematic diagram of the irreversible liquid metal material of temperature control phase transformation in terms of tumor vessel blocking.
Fig. 3 is application schematic diagram of the irreversible liquid metal material of temperature control phase transformation in terms of metal structure repairing.
Embodiment
To make the purpose, preparation scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is described.Obviously, described embodiment is a part of the invention
Embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making wound
The every other embodiment obtained under the premise of the property made work, belongs to the scope of protection of the invention.
The present invention is a kind of preparation method and applications of the porous liquid metal material of irreversible transition, by liquid metal gallium
Indium alloy is prepared as raw material, by adding iron powder and hydrochloric acid, is enriched with iron powder with magnetic field, heating or standing can reach
The structure of porous low-density, heating is changed into solid-state, and volumetric expansion from liquid, and temperature control is irreversible.Detailed process such as Fig. 1 institutes
Show, including：
Step one：Liquid metal 1 is gallium-indium alloy, and 10ml liquid metal 1 is placed in beaker 2, and in liquid gold
Belong to the 1 micro-nano ferrous powder granules 3 of surface spreading 2g, afterwards pour into the hydrochloric acid solution 4 of 9% mass fraction in beaker 2, until completely
Liquid metal 1 is submerged, stirring causes iron powder to consume completely in 5 minutes, and the liquid for getting rid of low magnetic is separated by 50 gauss magnetic fields
State metal, obtains ferromagnetism liquid metal 5.
Step 2：Ferromagnetism liquid metal 5.Redox reaction occurs in hydrochloric acid solution 4, substantial amounts of hydrogen 6 is produced,
Its expansion is set to form loose structure by heating ferromagnetism liquid metal 5, and heating to be changed into solid state from liquid, plus
The process of heat reacts
Ga2O+H2O→3H2+Ga2O3
Gallium-indium alloy can spontaneously form oxide, as long as in the case of having air and water, it is possible to endlessly produce
Raw hydrogen, can obtain the porous liquid metal material 7 of irreversible transition after volumetric expansion.
The specific embodiment of such a materials application is realized by the following method：
As shown in Fig. 2 the application in terms of tumor vessel blocking, the porous liquid metal material 7 of irreversible transition is in room temperature
Liquid condition is kept in environment, and raising temperature can promote it further to aoxidize, dress is changed to solid state, and reduces temperature
Liquid condition is not returned to.The porous liquid metal material 7 of irreversible transition is drawn into syringe 8 in an in vitro environment, by
Syringe 8 is injected into blood vessel 9.The porous liquid metal material 7 of irreversible transition is oxidized to solid in the higher blood vessel 9 of temperature
Body state, and expand, specific blood vessel 9 can be blocked, the nutrition supply for blocking tumour cell.
As shown in Fig. 2 the application in terms of metal structure repairing, the porous liquid metal material 7 of irreversible transition is in normal temperature
Viscous liquid state is in environment, specific shape can be easily fashioned into, the metal structure filled up in given shape lacks
Fall at 10；The heating porous liquid metal material 7 of irreversible transition aoxidizes it afterwards, solid state is converted into, with metal structure
The formation complete structure of defect 10.
To sum up, liquid metal internal of the present invention, which has, contains gas in loose structure, loose structure, normality is liquid, cooling
Or heating can be changed into solid phase from liquid phase, the solid metallic of high-density high-strength can be turned into after cooling, heating can also be by
Liquid is changed into loose porous solid metallic, cannot be changed into liquid condition by cooling again after heating, be by high-temperature process
Solid matter can be changed into by liquid is permanent, this material has porosity high, density is small, and good conductivity, insulation effect is good, it is stable
Property is good, the advantages of excellent magnetic, also with metal material the characteristics of, this high temperature causes liquid-solid-phase changeable to break traditional phase transformation
Principle, and heating treatment can allow the material of liquid permanent cured, and this material combines many excellent properties, in electronics
Industry, internal robot, magnetic control drives, and there is important application in the field such as metal mending.
Above-described is only the preferred embodiment of the invention, it is noted that for the ordinary skill people of the art
For member, on the premise of the technology of the present invention principle is departed from, some improvement and replacement can also be made, these improve and replaced
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of porous liquid metal material of temperature control irreversible transition, it is characterised in that liquid metal internal has loose structure, many
Contain gas in pore structure, normality is liquid, and cooling or heating can be changed into solid phase from liquid phase.
2. the porous liquid metal material of temperature control irreversible transition according to claim 1, it is characterised in that the liquid metal
For gallium base series alloy, the gas is hydrogen.
3. the porous liquid metal material of temperature control irreversible transition according to claim 1, it is characterised in that the cooling is drop
Temperature is to freezing point, and the heating is to be warming up to 50 degrees Celsius or more, and normality refers to room temperature normal pressure.
4. the porous liquid metal material of temperature control irreversible transition according to claim 3, it is characterised in that the soft gold of solid phase
The intensity of category is by acid-base value control, when under alkaline environment, intensity increases.
5. the porous liquid metal material of temperature control irreversible transition according to claim 1, it is characterised in that density subtracts after heating
It is small, enabling to swim in the water surface and ethanol surface.
6. the porous liquid metal material of temperature control irreversible transition according to claim 1, it is characterised in that in static conditions
Under, elapse over time, after 3-5 hours, liquid gradually becomes solid-state.
7. the preparation method of the porous liquid metal material of temperature control irreversible transition described in claim 1, it is characterised in that including such as
Lower step：
Step 1：In the micro-nano ferrous powder granules of liquid metal surface spreading, hydrochloric acid is added afterwards until being totally submerged liquid metal,
Stirring causes iron powder to consume completely, and the liquid metal for getting rid of low magnetic is separated by magnetic field, obtains ferromagnetism liquid metal；
Step 2：Redox reaction occurs in hydrochloric acid for ferromagnetism liquid metal, a large amount of hydrogen is produced, by heating ferromagnetism
Liquid metal makes its expansion form loose structure.
8. the preparation method of the porous liquid metal material of temperature control irreversible transition according to claim 7, it is characterised in that institute
State in step 1, the mass ratio of liquid metal and micro-nano ferrous powder granules is (10:1)~(2；1), Hydrochloric acid adequate amount；Magnetic field intensity 50
More than Gauss, adsorb and be continuing with ferromagnetism liquid metal, weak magnetic liquid metal return to step 1.
9. the preparation method of the porous liquid metal material of temperature control irreversible transition according to claim 7, it is characterised in that institute
It is 15% to state micro-nano ferrous powder granules mass content in the material that step 2 is obtained.
10. the porous liquid metal material of temperature control irreversible transition described in claim 1 is used as blood vessel blockage, drug delivering material
Purposes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841694A (en) * | 2017-10-30 | 2018-03-27 | 清华大学 | Controllable liquid metal complex fiber material of a kind of rigidity and preparation method thereof |
| CN108451995A (en) * | 2018-02-12 | 2018-08-28 | 邵辉 | A kind of preparation method of the smokeless wormwood based on low-temperature carbonization |
| CN108525128A (en) * | 2018-03-26 | 2018-09-14 | 清华大学 | Application of the liquid metal as tumour magnetic thermotherapy medium |
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