CN105784703B - A kind of insoluble nm-humidity instruction material and its preparation and application - Google Patents
A kind of insoluble nm-humidity instruction material and its preparation and application Download PDFInfo
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- CN105784703B CN105784703B CN201410821958.7A CN201410821958A CN105784703B CN 105784703 B CN105784703 B CN 105784703B CN 201410821958 A CN201410821958 A CN 201410821958A CN 105784703 B CN105784703 B CN 105784703B
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Abstract
The present invention provides one kind can serve to indicate that humidity, nm-humidity instruction material not soluble in water, and being recycled for multiple times.The material has the characteristics that safe and nontoxic, not soluble in water using the Prussian blue similar objects of nano Co Co as main component.It is sapphire blue color when dry, according to air humidity difference, can be gradually changed into after moisture absorption：Darkviolet, bluish violet, aubergine, it is pink.Also, it can be mixed colours it, then can be prepared with the nm-humidity instruction material for not having to instruction color by the doping of different transition metal (Cu, Fe, Mn, Ni, Zn).In addition, color change is apparent after the drying of such humidity indication material and moisture absorption, and color category is more, therefore can be used for preparing the fields such as invisible ink, painting layer.Change colour after such humidity indication material Color tunable, moisture absorption apparent, not soluble in water, therefore, has many advantages, such as that high sensitivity, recycling be strong, safety non-pollution.
Description
Technical field
The present invention relates to one kind can serve to indicate that humidity, not soluble in water, and the nanometer that can be recycled for multiple times is wet
Degree instruction material.
Background technology
Humidity indication material currently on the market, such as humidity indicating card, discoloration silica gel etc., mostly using cobalt chloride as instruction
Agent.Such indicator can indicate humidity by becoming the color change of pink by blue.And on October 28th, 2008,
The European chemicals Room (ECHA) discloses 15 kinds of chemical substances of REACH regulation height concern substance (SVHC) first batch.Chlorination
Cobalt list in this 15 chemical substances in the 4th.Therefore, start novel humidity instruction material, root gradually occur in the market
If the first specified chemical substance is less than 1.00% according to PRTR law regulations, so that it may with not according to the control of PRTR methods to that way into
Row is declared, therefore, a kind of to be commonly called as being used all the year round for the commodity of the blue glue of mixing containing about 0.1% cobalt chloride detection agent.Although
Its chlorination cobalt content is very low, but cobalt chloride is highly soluble in water, indicate certainly will to have while humidity part it is molten in water, and can
Can occur being eaten etc. by mistake the case where being detrimental to health by people.
In addition, a part of humidity indicator without cobalt in the market, the variation of mainly yellowish green color, it is this by it is dry when
Yellow become water suction after green be not obvious, therefore, the sensitivity of this kind of humidity indicator is not high.Therefore, city at present
Also it is badly in need of finding a kind of can substituting cobalt chloride, the apparent humidity indication material of color change on field.
Invention content
The present invention provides one kind can serve to indicate that humidity, nanometer not soluble in water, and being recycled for multiple times
Humidity indication material.The material belongs to Prussian blue similar object, and it is Prussian blue then once clothes coloring, dyestuff, ink and
The fields such as radioactive cesium waste water absorption are widely applied.Therefore, which equally has similar Prussian blue property, peace
Entirely, nontoxic.It is provided by the invention
Insoluble nm-humidity indicates that material, ingredient are that six cyanogen close cobalt acid cobalt, undope or containing transition metal Cu, Fe,
Any one in Mn, Ni or Zn or two kinds or more, can pass through the color of containing transition metal modulation material；Its chemical formula
For：CoxMy[Co(CN)6]0.66, wherein M is any one or two kinds or more in above-mentioned transition metal, x=0.5~1, y=0
~0.5.
When M is 0, under different air humiditys, the color of material can change；It is sapphire blue face when dry
Color from low to high according to moisture absorption degree can gradually be changed into after moisture absorption：Darkviolet, bluish violet, aubergine, it is pink.
The face of original material can be changed by the doping of the transition metal of different transition metal or different content
Color, and color change different after there is moisture absorption；Ni3[Co(CN)6]2/Cu3[Co(CN)6]2,Mn3[Co(CN)6]2/Zn3[Co
(CN)6]2,Fe3[Co(CN)6]2And Co3[Co(CN)6]2Material for priming color be successively：Blue, white, yellow and red
Color.
The preparation process of above-mentioned material is as follows：
1) by the K of 1~100mmol/L of final concentration3[Co(CN)6] be dissolved in deionized water, stirring is to being completely dissolved；
2) it by final concentration 1~200mmol/L Co ions presoma, final concentration 0~200mmol/L transition metal salts, is dissolved in
In deionized water, stirring is to being completely dissolved；
3) above-mentioned two solution is slowly mixed together in equal volume, the sum of Co ions presoma and transition metal salinity in mixed liquor
For K3[Co(CN)6] 1.5~3 times of concentration；10~120min is stirred, Co is generatedxMy[Co(CN)6]0.66Nano material (M Cu,
Any one in Fe, Mn, Ni or Zn, x=0.5~1, y=0~0.5)；
4) aging is stood, solid product is detached.
The Co ions presoma is one kind or two kinds in cobalt chloride, cobalt nitrate or cobaltous sulfate, the transition metal salt
For in the chloride, nitrate or sulfate of any one or two kinds or more in Cu, Fe, Mn, Ni or Zn one kind or two kinds
More than；Ageing time is 12-20h；It is described separation solid product method be centrifugation, in water or ethyl alcohol one kind or two kinds wash
It washs, it is dry.It is above-mentioned insoluble
Nm-humidity indicates that material can obtain extensively in indicating humidity, preparing invisible ink or preparation discoloration silica gel
Application.
Such humidity indication material closes cobalt acid cobalt (Co-Co PBA) as main component with six cyanogen, is sapphire blue when dry
Color from low to high according to air humidity can gradually be changed into after water suction：Darkviolet, bluish violet, aubergine, it is pink.Cause
This, can be used to refer to different humidity.Also, can by the doping of different transition metal (Cu, Fe, Mn, Ni, Zn) to its into
Row toning can then prepare the nm-humidity with different instruction colors and indicate material.Such humidity indication material Color tunable is inhaled
It is wet after discoloration it is apparent, not soluble in water, therefore, have many advantages, such as high sensitivity, recycling by force, safety non-pollution.
Such nanochromics material is not soluble in water, therefore, after moisture absorption not easily runs off on environment or food, therefore more
Add safety and environmental protection.
Since humidity instruction nano material color change under different humidity is apparent, humidity instruction can be used for
Card, discoloration silica gel etc. need the field of color change instruction humidity.In addition, after due to the drying of such humidity indication material and moisture absorption
Color change is apparent, and color category is more, therefore can be used for preparing the fields such as invisible ink, painting layer.
Description of the drawings
Fig. 1 is that six cyanogen of the different iron contents described in embodiment 3-5 close cobalt acid cobalt nm-humidity indicator, in different suctions
Color change photo under humidity.It can be seen from the figure that under different wettabilities, each nm-humidity indicator can be sent out
Raw corresponding color variation, and then sensitively indicate humidity.Furthermore it is possible to it is different by the content that transition metal is added, it can adjust
Become indicator in dry and moisture absorption color.
Fig. 2 is the design sketch of the invisible ink described in embodiment 6.After being write on pink paper with the ink, material
Material, which absorbs the moisture in air, can become pink, therefore can achieve the effect that stealthy word.After the purging drying of hot wind, by
In the color shifting properties of material, and reappear the font for showing blue.
Specific implementation mode
Embodiment 1
Chemical formula is Co0.5Fe0.5[Co(CN)6]0.66Insoluble nm-humidity instruction material preparation：
1) by concrete numerical value 5mmol/L K3[Co(CN)6] be dissolved in 20ml ionized waters, stirring is to being completely dissolved.
2) by 5mmol/L Co (NO)3·6H2O and 5mmol/L FeCl2·4H2O is dissolved in 20ml deionized waters, stirring
To being completely dissolved；Above-mentioned two solution is slowly mixed together in equal volume, stirs 30min afterwards, generates Co0.5Fe0.5[Co(CN)6]0.66Nanometer
Material；
3) aging 20h is stood, 8000r/min centrifuges 6min, with volume ratio about 1：1 water and alcohol mixeding liquid washing, does
The dry chemical formula that obtains is Co0.5Fe0.5[Co(CN)6]0.66Insoluble nm-humidity instruction material preparation：
Embodiment 2
The different transient metal doped influences to priming color and moisture absorption color are investigated, it is different with reference to the method for embodiment 1
Place is to replace precursor solution (nitrate, the sulfate of Fe with other transition metal (Cu, Mn, Ni or Zn) presoma
Or chloride etc.), Co is prepared respectively0.5M0.5[Co(CN)6]0.66, M Cu, Mn, Ni or Zn are one or more kinds of.Its phase
It should dry as shown in the table with moisture absorption color：
Embodiment 3
The humidity indicator that cobalt acid cobalt doped difference transition metal is main material is closed using six cyanogen, with different Fe2O3 doping amounts
Six cyanogen close cobalt acid cobalt for, with reference to embodiment 1 method, the difference is that change two kinds of solution concentration, prepare respectively
Its chemical formula is CoxFey[Co(CN)6]0.66, y/ (x+y)=0,0.1,0.2,0.3,0.4,0.5, what specific x, y value see the table below
Humidity indication material；It is dried and moisture absorption color is as shown in the table：
Color is moisture absorption color to greatest extent after moisture absorption described in upper table.In addition, color may be due to the collimation error
Description may slightly have difference.According to the difference of Fe2O3 doping amount, material is different with the color change after moisture absorption in drying, therefore can be with
Prepare the humidity indication material of different colours variation.
Embodiment 4
In material provided by the invention under different moisture absorption degree, color also differs, and variation is apparent.With Co [Co
(CN)6]0.66For material, under different moisture absorption degree, color is as shown in the table：
Embodiment 5
In material provided by the invention, after adulterating different amounts of transition metal, also have under different humidity different
Color.With Co0.9Fe0.1[Co(CN)6]0.66For, in different moisture absorption degree, color is as shown in the table：
The present invention can also adulterate other different types of transition metal, so that the discoloration face after its drying and moisture absorption
Color changes.
Embodiment 6
By Co [Co (CN)6]0.66It is simply dispersed in ethanol solution, invisible ink can be prepared as.With the ink pink
After writing on the paper of color, material, which absorbs the moisture in air, can become pink, therefore can achieve the effect that stealthy word.In heat
After the purging drying of wind, due to the color shifting properties of material, and the font for showing blue is reappeared.Therefore, which is possibly used for
Prepare the fields such as invisible ink.
It is configured to solution with such nm-humidity instruction material prepared, impregnates paper, bonded fabric or other fibres afterwards
Class material is tieed up, the card with humidity indicating function, referred to as humidity indicating card can be made；Also back loading or leaching can be prepared
Stain silica gel obtains the discoloration silica gel with different colours colour change function.Carrier well known to those skilled in the art can also be point
Sub- sieve, aluminium oxide, bentonite etc..
It is only the preferred embodiment of the present invention to be given above, and those skilled in the art is after reading the present invention, very
It is easy that the present invention is made modification and is more than the scope of protection of present invention, applicant is intentionally by these obvious modifications
It is included within the scope of the invention.
Claims (5)
1. a kind of insoluble nm-humidity indicates material, it is characterised in that：
Ingredient is that six cyanogen close cobalt acid cobalt, one or more in containing transition metal Cu, Fe, Mn, Ni or Zn, can pass through doping
The color of transition metal modulation material；Its chemical formula is：CoxMy[Co(CN)6]0.66, wherein M is one in above-mentioned transition metal
Kind or a variety of, x=0.5~1, y=0~0.5 and y ≠ 0.
2. nm-humidity described in accordance with the claim 1 indicates material, it is characterised in that：
The color of original material can be changed by the doping of the transition metal of different transition metal or different content, and
Different color change after appearance moisture absorption；Co0.5Ni0.5[Co(CN)6]0.66And Co0.5Cu0.5[Co(CN)6]0.66Priming color is
Puce, Co0.5Mn0.5[Co(CN)6]0.66And Co0.5Zn0.5[Co(CN)6]0.66Priming color is lilac, Co0.5Fe0.5[Co
(CN)6]0.66Priming color is celadon.
3. a kind of preparation method of any insoluble nm-humidity instruction materials of claim 1-2, it is characterised in that：
Its preparation process is as follows：
1) by the K of 1~100mmol/L of final concentration3[Co(CN)6] be dissolved in deionized water, stirring is to being completely dissolved；
2) by final concentration 1~200mmol/L Co ions presoma, final concentration 5~200mmol/L transition metal salts, be dissolved in from
In sub- water, stirring is to being completely dissolved；
3) above-mentioned two solution is slowly mixed together, the sum of Co ions presoma and transition metal salinity are K in mixed liquor3[Co
(CN)6] 1.5~3 times of concentration；10~120min is stirred, Co is generatedxMy[Co(CN)6]0.66Nano material, wherein M be Cu, Fe,
It is one or more in Mn, Ni or Zn, x=0.5~1, y=0~0.5 and y ≠ 0；
4) aging is stood, solid product is detached.
4. preparation method described in accordance with the claim 3, it is characterised in that：
The Co ions presoma is one kind or two kinds in cobalt chloride, cobalt nitrate or cobaltous sulfate, and the transition metal salt is M's
One or more in chloride, nitrate or sulfate, wherein M is one or more in Cu, Fe, Mn, Ni or Zn；Aging
Time is 12-20h；The method of the separation solid product is centrifugation, in water or ethyl alcohol one kind or two kinds of washings, it is dry.
5. a kind of any insoluble nm-humidity instruction material of claim 1-2 instruction humidity, prepare invisible ink or
Prepare the application in discoloration silica gel.
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|---|---|---|---|
| CN201410821958.7A CN105784703B (en) | 2014-12-24 | 2014-12-24 | A kind of insoluble nm-humidity instruction material and its preparation and application |
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| CN105784703B true CN105784703B (en) | 2018-07-20 |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1091987A (en) * | 1976-11-24 | 1980-12-23 | Bernard Slepak | Moisture indicator |
| GB2119659B (en) * | 1982-04-28 | 1985-10-02 | Mine Safety Appliances Co | Breathing device having irreversible moisture indicator |
| JP2543837B2 (en) * | 1987-12-11 | 1996-10-16 | 大日本印刷株式会社 | Humidity indicator |
| GB9909219D0 (en) * | 1999-04-22 | 1999-06-16 | Crosfield Joseph & Sons | Humidity indicators |
| IT1313584B1 (en) * | 1999-07-30 | 2002-09-09 | Levosil S P A | HUMIDITY INDICATORS TO INDICATE THE ABSORBING CAPACITY OF A DEHYDRATING MATERIAL. |
| CN101393134A (en) * | 2008-10-23 | 2009-03-25 | 杨德成 | Humidity indicators |
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2014
- 2014-12-24 CN CN201410821958.7A patent/CN105784703B/en not_active Expired - Fee Related
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