CN107476129A - A kind of high temperature resistant fire resisting compliant conductive paper and its application based on hydroxyapatite overlong nanowire - Google Patents
A kind of high temperature resistant fire resisting compliant conductive paper and its application based on hydroxyapatite overlong nanowire Download PDFInfo
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- CN107476129A CN107476129A CN201710692901.5A CN201710692901A CN107476129A CN 107476129 A CN107476129 A CN 107476129A CN 201710692901 A CN201710692901 A CN 201710692901A CN 107476129 A CN107476129 A CN 107476129A
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- high temperature
- temperature resistant
- fire resisting
- resistant fire
- conductive paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
Abstract
The present invention relates to a kind of high temperature resistant fire resisting compliant conductive paper based on hydroxyapatite overlong nanowire and its application, the composition of the high temperature resistant fire resisting compliant conductive paper includes hydroxyapatite overlong nanowire and conductive filler, the conductive filler includes conductive black or/and conducting metal particles, and mass percent of the conductive filler in high temperature resistant fire resisting compliant conductive paper is 1~70%.
Description
Technical field
The invention belongs to nano material and conductive material field, is related to a kind of based on the resistance to of hydroxyapatite overlong nanowire
High-temperature flame-proof compliant conductive paper and its application.
Background technology
Flexible electronic devices, such as conductive paper, conductive fabric, conductive elastomer etc., wearable device, electronic skin,
The various fields such as battery electrode, touch-screen, electric heater, antistatic, electromagnetic shielding, antibacterial, anti-icing and deicing all have extensive
Using.
In a variety of applications, flexible electronic devices need to contact different external environments.However, external environment because
Element often reduces the performance of flexible electronic devices, or even produces the destruction of unrepairable.For example, the touch screen of mobile phone is being met
Can not effectively be operated after water, the situation that its internal electronic component is stopped or damaged after mobile phone water inlet also when have hair
It is raw；For another example, in electronic equipment because in electrical fire caused by short circuit, excessive, the improper operation of load, electronic equipment is also difficult to protect
Hold normal operation；Ice and snow environment also generates acid test to electronic equipment, such as 2008 ice and snow calamities occurred in China
The power transmission network that evil causes large area caves in.
In some reports, such as a kind of patent " preparation method of cellulose base compliant conductive paper " (application number：
201610917179.6), " a kind of conductive paper and preparation method thereof " (application number：201610050870.9), " nanofiber carbon black
Conductive paper and preparation method thereof " (application number：201611250745.9), base material used is with flammable and non-refractory
String.Although string is advantageous to improve the pliability of conductive paper, but its inflammability, resistance to elevated temperatures are poor and easily wet
Property makes it be difficult in adapt to the application of various environment.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of new based on hydroxyapatite overlong nanowire
High temperature resistant fire resisting compliant conductive paper and its application.
On the one hand, the invention provides a kind of high temperature resistant fire resisting compliant conductive based on hydroxyapatite overlong nanowire
Paper, the composition of the high temperature resistant fire resisting compliant conductive paper include hydroxyapatite overlong nanowire and conductive filler, the conduction
Filler is conductive black or/and conducting metal particles, quality hundred of the conductive filler in high temperature resistant fire resisting compliant conductive paper
Fraction is 1~70%, preferably 10~40%.
The present invention uses base material of the hydroxyapatite overlong nanowire as incombustible paper, (conductive by adding conductive filler
Carbon black or/and conducting metal particles) obtain high temperature resistant fire resisting compliant conductive paper.Adding conductive filler not only makes hydroxyapatite resistance to
Touch paper is conductive can, additionally it is possible to improves the multilevel hierarchy of hydroxyapatite overlong nanowire incombustible paper, is carrying out follow-up
After dimethyl silicone polymer applies stratification processing, its hydrophobicity is significantly improved, reaches super-hydrophobicity.If conductive filler content exceedes
70wt%, the mechanical strength poor performance of high temperature resistant fire resisting compliant conductive paper of the gained based on hydroxyapatite overlong nanowire；
If conductive filler content is less than 10wt%, high temperature resistant fire resisting compliant conductive paper of the gained based on hydroxyapatite overlong nanowire
Electric conductivity it is poor.
It is preferred that the high temperature resistant fire resisting compliant conductive paper surface can also coat dimethyl silicone polymer super-hydrophobic layer, institute
The thickness for stating dimethyl silicone polymer super-hydrophobic layer is 1~100 micron, preferably 5~20 microns.Use dimethyl silicone polymer
Conductive paper is carried out after applying stratification processing, the compliant conductive paper of super hydrophobic high temperature fire resisting is obtained, high temperature resistant fire resisting can be made soft
Property conductive paper increase waterproof, damp proof, moisture-proof function.
Also, soaked it is preferred that the high temperature resistant fire resisting compliant conductive paper is positioned in dimethyl silicone polymer dilution
After 10~200 minutes, solidify 0.1~24 hour at 50~200 DEG C, obtain the resistance to height that surface is coated with dimethyl silicone polymer
Warm fire resisting compliant conductive paper.It is preferred that dimethyl silicone polymer, curing agent and acetic acid in the dimethyl silicone polymer dilution
The mass ratio of ethyl ester is (5~15): (0.5~1.5): (50~150), preferably 10: 1: 100.
It is preferred that the particle diameter of the conductive filler is 10 nanometers~100 microns, the preferable conducting metal particles include
At least one of Au, Pt, Ag, Cu, Al and Fe.
It is preferred that the length of the hydroxyapatite overlong nanowire be 20~2000 microns, it is a diameter of 5~100 nanometers.
It is preferred that the thickness of the high temperature resistant fire resisting compliant conductive paper is 10~3000 microns.
Second aspect, present invention also offers a kind of resistance to based on the above-mentioned high temperature resistant based on hydroxyapatite overlong nanowire
The electric heater of fiery compliant conductive paper.Heretofore described high temperature resistant fire resisting compliant conductive paper after application of a voltage, compliant conductive
The temperature of paper rapid increase within a short period of time.
The third aspect, present invention also offers a kind of high temperature resistant as described above based on hydroxyapatite overlong nanowire is resistance to
Fiery compliant conductive paper is in waterproof, fire resisting, high temperature resistant, damp proof protection against the tide, anti-icing and deicing, high temperature resistant fire resisting flexible PCB, high temperature resistant
Application in fire resisting flexible electronic device.
The beneficial effects of the present invention are：The present invention is using hydroxyapatite overlong nanowire as base material, by simple
The preparation method of mixing-suction filtration-coating obtains high temperature resistant fire resisting compliant conductive paper.Simple preparation method, original cheap and easy to get
Material, stable performance make the hydroxyapatite nano line high temperature resistant fire resisting compliant conductive paper have good answer in numerous areas
It is high temperature resistant conductive paper, high temperature resistant fire resisting waterproof conductive paper, waterproof, damp proof with prospect, such as waterproof conductive paper, fire resisting conductive paper
The fields such as protection against the tide, anti-icing and deicing, electric heater, high temperature resistant fire resisting flexible PCB, high temperature resistant fire resisting flexible electronic product.
Brief description of the drawings
Fig. 1 is the transmission electron microscopy figure of hydroxyapatite overlong nanowire prepared by embodiment 1；
Fig. 2 is the transmission electron microscopy figure of conductive filler-conductive black used in embodiment 2 and 3；
Fig. 3 is that hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3 connects into electricity with LED
Road；
Fig. 4 is the water contact angle test of hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3；
Fig. 5 is the scanning electron microscopy of hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3
Figure；
Fig. 6 and Fig. 7 is the scanning electron microscopy of hydroxyapatite overlong nanowire high temperature resistant fire resisting flexible paper prepared by embodiment 4
Figure；Fig. 8 is the water contact angle test of hydroxyapatite overlong nanowire high temperature resistant fire resisting flexible paper prepared by embodiment 4；
Fig. 9 is that the temperature of compliant conductive paper becomes after applying DC voltage to high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3
Change；
Figure 10 is led for high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3 is immersed in water by high temperature resistant fire resisting flexibility
The real-time current of electric paper；
Figure 11 is that the waterproof heat-resisting fire resisting compliant conductive paper being immersed in water and LED are connected into circuit, is soaked 120 seconds
Afterwards, the running situation of LED；
Figure 12 is that high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3 is placed on into calcination in fire, passes through the reality of compliant conductive paper
When electric current；
Figure 13 is that the high temperature resistant fire resisting compliant conductive paper of the calcination in fire and LED connected into circuit, after calcination 420 seconds, LED
The running situation of lamp；
Figure 14 is that ice cube is placed on to the dynamic change after applying alive waterproof heat-resisting fire resisting compliant conductive paper surface.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
Heretofore described high temperature resistant fire resisting compliant conductive paper (the high temperature resistant fire resisting based on hydroxyapatite overlong nanowire
Compliant conductive paper) composition include hydroxyapatite overlong nanowire and conductive filler, the conductive filler be conductive black or/
And conducting metal particles, mass percent of the conductive filler in high temperature resistant fire resisting compliant conductive paper can be 1~70%, excellent
Elect 10~40% as.The thickness of the compliant conductive paper can be 10~3000 microns.
In the present invention, the high temperature resistant fire resisting compliant conductive paper surface can also coat dimethyl silicone polymer super-hydrophobic layer,
The thickness of the dimethyl silicone polymer super-hydrophobic layer can be 1~100 micron.Conductive paper is carried out using dimethyl silicone polymer
After applying stratification processing, obtaining super hydrophobic high temperature fire resisting compliant conductive paper, (that is, described high temperature resistant fire resisting compliant conductive paper can have
Water resistance or super-hydrophobicity) so that high temperature resistant fire resisting compliant conductive paper increase waterproof, damp proof, moisture-proof function.In addition, tool
The high temperature resistant fire resisting compliant conductive paper for having water-proof function also can steady operation in water.
In the present invention, the length of the hydroxyapatite overlong nanowire can be 20~2000 microns, a diameter of 5~100
Nanometer.Primary raw material of the hydroxyapatite overlong nanowire as high temperature resistant fire resisting compliant conductive paper, has advantages below：(1)
Hydroxyapatite is calcium phosphate inorganic bio, is the main inorganic composition of vertebrate skeletal and tooth, is had excellent
Biocompatibility and bioactivity；(2) inorganic material is used as, hydroxyapatite has excellent heat endurance, can play
High temperature resistant, the function of fire resisting；(3) hydroxyapatite overlong nanowire has the length of overlength and the draw ratio of superelevation, has height
Pliability, be advantageous to obtain high temperature resistant fire resisting flexible paper.
In the present invention, the conductive filler includes conductive black or/and conducting metal particles.The conducting metal particles bag
Include at least one of Au, Pt, Ag, Cu, Al and Fe.The particle diameter of the conductive filler can be 10 nanometers~100 microns.
Illustrate to following exemplary that the high temperature resistant fire resisting provided by the invention based on hydroxyapatite overlong nanowire is flexible
The preparation method of conductive paper.
The preparation of hydroxyapatite overlong nanowire.Hydroxyapatite overlong nanowire of the present invention can use fat
Prepared by sour calcium presoma solvent-thermal method or hydro-thermal method, refer to the patent of invention before inventor, such as：Zhu Yingjie, Lu Bingqiang,
Chen Feng, the non-ignitable hydroxyapatite paper of high-flexibility high temperature resistant and preparation method thereof, patent No. ZL201310687363.2；Zhu Ying
Outstanding person, Li Heng, Wu Jin, hydroxyapatite nano line, nano wire assembling network structure and preparation method thereof, application number:
201611095409.1.Also other suitable preparation methods can be used, as long as method therefor can prepare the hydroxy-apatite
Stone overlong nanowire.
Hydroxyapatite overlong nanowire dispersion liquid and conductive filler dispersion liquid (are controlled into the conduction according to a certain ratio
Mass percent of the filler in high temperature resistant fire resisting compliant conductive paper is between 1~70%, and preferably 10~40%), stirring is equal
After even, paper making pulp is obtained.The solvent of the hydroxyapatite overlong nanowire dispersion liquid or/and conductive filler dispersion liquid can be
Water or/and alcohol etc..The alcohol includes methanol, ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol etc..The stirring means
It can be magnetic agitation, mechanical agitation, to agitating mode without particular/special requirement, be well mixed.
Paper making pulp is removed into water removal or alcohol through filtering, it is resistance into the high temperature resistant based on hydroxyapatite overlong nanowire after drying
Fiery compliant conductive paper.The temperature of the drying can be 10~200 DEG C, and the time can be 0.01~24 hour.
In the present invention, the high temperature resistant fire resisting compliant conductive paper surface can use dimethyl silicone polymer moditied processing,
It is increased super-hydrophobicity and water resistance, realize compliant conductive paper while there is the performance of waterproof, high temperature resistant, fire resisting, conduction,
Compliant conductive paper can keep good electrical property in water and fire.Specifically, by obtained high temperature resistant fire resisting made above
Compliant conductive paper is immersed in dimethyl silicone polymer, is carried out dimethyl silicone polymer coating, is then placed compliant conductive paper
Make its solidification.As an example, the high temperature resistant fire resisting compliant conductive paper is positioned in dimethyl silicone polymer dilution
After immersion 10~200 minutes, solidify 0.1~24 hour at 50~200 DEG C, obtain surface and be coated with dimethyl silicone polymer
High temperature resistant fire resisting compliant conductive paper.Dimethyl silicone polymer, curing agent and solvent in the dimethyl silicone polymer dilution
Mass ratio can be (5~15): (0.5~1.5): (50~150), preferably 10: 1: 100.
In the present invention, the high temperature resistant fire resisting compliant conductive paper based on hydroxyapatite overlong nanowire, have excellent
Performance, such as should be led based on hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper in waterproof conductive paper, fire resisting
Electric paper, high temperature resistant conductive paper, high temperature resistant fire resisting waterproof conductive paper, waterproof, damp proof protection against the tide, anti-icing and deicing, electric heater, high temperature resistant
Application in the fields such as fire resisting flexible PCB, high temperature resistant fire resisting flexible electronic product.
In the present invention, described high temperature resistant fire resisting compliant conductive paper has high temperature resistant fire resistance.High temperature resistant fire resisting is soft
Property conductive paper be placed on calcination in fire (temperature can be 500~1000 DEG C), the performance of compliant conductive paper is relatively stable, can be smoothly
For power electronic equipment.
In the present invention, described high temperature resistant fire resisting compliant conductive paper has anti-icing and deicing ability.It is flexible to high temperature resistant fire resisting
The ice cube that caused heat can be on fast melt paper after conductive paper time voltage, ice-out Cheng Shuihou are resistance to by means of high temperature resistant
The water resistance (super-hydrophobicity) of fiery compliant conductive paper, the water of thawing quickly tumble from paper.
In the present invention, the high temperature resistant fire resisting compliant conductive paper can produce enough heats in the case where applying voltage, improve
The temperature of high temperature resistant fire resisting compliant conductive paper.Therefore, the invention provides a kind of above-mentioned high temperature resistant fire resisting compliant conductive paper in electricity
Application in heater.The operating method of electric heater based on high temperature resistant fire resisting compliant conductive paper is as follows：(1) it is resistance in high temperature resistant
The both ends cladding copper foil and elargol water of fiery compliant conductive paper；(2) direct current is applied to high temperature resistant fire resisting compliant conductive paper by wire
Voltage；(3) after applying voltage, the temperature of high temperature resistant fire resisting compliant conductive paper steeply rises in a short time.The DC voltage
Can be 0~50V, preferably 5~20V.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.The present invention is using commodity polydimethylsiloxanes
Alkane, including prepolymer and curing agent, prepolymer are 184A, and curing agent is 184B.Wherein solvent is ethyl acetate, is dilution
The preferable solvent of dimethyl silicone polymer.
Embodiment 1：The synthesis of hydroxyapatite overlong nanowire
140.0g ethanol and 100.0g oleic acid are stirred, add the aqueous solution of 200mL calcium chloride containing 2.200g；Stirring 20
After minute, the aqueous solution of 200mL sodium hydroxides containing 10.000g is added；After stirring 20 minutes, 100mL water containing 2.800g bis- is added
The aqueous solution of sodium dihydrogen phosphate is closed, continues stirring 20 minutes；Gained mixture is transferred in reactor, seals, is heated to 180
DEG C, it is incubated 24 hours.Products therefrom is cleaned repeatedly with second alcohol and water respectively, obtains hydroxyapatite overlong nanowire, such as Fig. 1
Shown, the length of the hydroxyapatite overlong nanowire is 20~2000 microns, a diameter of 5~100 nanometers.
Embodiment 2：The preparation of hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper
Conductive filler-conductive black used is as shown in Figure 2.The ethanol solution of the conductive black containing 10mg and the phosphorus of hydroxyl containing 40mg
The ethanol solution mixing of lime stone overlong nanowire, magnetic agitation are filtered after 10 minutes and remove ethanol, and 5 are dried on 90 DEG C of hot plates
Minute, obtained high temperature resistant fire resisting compliant conductive paper.The water of prepared high temperature resistant fire resisting compliant conductive paper connects in this embodiment
Feeler is~0 °.
Embodiment 3：The preparation of hydroxyapatite overlong nanowire super hydrophobic high temperature fire resisting compliant conductive paper
Conductive filler-conductive black used is as shown in Figure 2.High temperature resistant fire resisting compliant conductive paper prepared by embodiment 2 is placed
Soaked 30 minutes in dimethyl silicone polymer dilution.The mass ratio of dimethyl silicone polymer dilution is：Poly dimethyl silicon
Oxygen alkane: curing agent: ethyl acetate=10: 1: 100.After immersion terminates, the high temperature resistant fire resisting of dimethyl silicone polymer will be coated with
Compliant conductive paper, which is placed at 100 DEG C, to be solidified 1 hour, and it is~98 microns of waterproof heat-resisting fire resisting compliant conductive paper to obtain thickness.
Waterproof heat-resisting fire resisting compliant conductive paper and LED are connected into circuit, LED sends light (Fig. 3), it is good to illustrate that it has
Good electric conductivity.The electrical conductivity of prepared waterproof heat-resisting fire resisting compliant conductive paper is 21.0 S/m in this embodiment, and water connects
Feeler is~151 °, sees Fig. 4.Its microstructure is shown in Fig. 5.
Embodiment 4：The preparation of hydroxyapatite overlong nanowire super hydrophobic high temperature incombustible paper
The ethanol solution of the overlong nanowire of hydroxyapatite containing 50mg filters, and is dried 5 minutes on 90 DEG C of hot plates, obtained resistance to height
Warm fire resisting flexible paper (Fig. 6).High temperature resistant fire resisting flexible paper is placed in dimethyl silicone polymer dilution and soaked 30 minutes.It is poly-
The mass ratio of dimethyl siloxane dilution is：Dimethyl silicone polymer: curing agent: ethyl acetate=10: 1: 100.Immersion knot
Shu Hou, the high temperature resistant fire resisting compliant conductive paper for being coated with dimethyl silicone polymer is placed at 100 DEG C and solidified 1 hour, is obtained
Thickness is~81 microns of waterproof heat-resisting fire resisting flexible papers (Fig. 7).Prepared waterproof heat-resisting fire resisting is flexible in this embodiment
The electric water contact angle of conductive paper is~137 ° (Fig. 8).The super-hydrophobic resistance to height of hydroxyapatite overlong nanowire prepared with embodiment 3
Warm fire resisting compliant conductive paper contrast, water contact angle are significantly reduced, and comparison diagram 6 and Fig. 7 are understood, carry out dimethyl silicone polymer coating
After change processing, surface becomes smooth.After adding conductive filler, hydroxyapatite overlong nanowire super hydrophobic high temperature can be improved
The multilevel hierarchy of fire resisting compliant conductive paper.Therefore, adding conductive filler not only has hydroxyapatite overlong nanowire incombustible paper
Have conductivity, moreover it is possible to make after carrying out dimethyl silicone polymer and applying stratification processing, significantly improve hydrophobicity, reach super-hydrophobic
Property.
Embodiment 5：Electric heater based on hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper
Copper foil is wrapped up in the both sides of the hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3,
DC voltage is applied to high temperature resistant fire resisting compliant conductive paper by wire, the temperature of high temperature resistant fire resisting compliant conductive paper is in the short time
Inside sharply increase, adjustment DC voltage can control the temperature on high temperature resistant fire resisting compliant conductive paper surface, as shown in Figure 9.Direct current
When voltage is 10,15,20V, temperature of the compliant conductive paper at 9.6 seconds is 86.3 DEG C, 153.3 DEG C, 224.3 DEG C respectively.As a result
It can be seen that at lower voltages, the efficiency of heating surface of high temperature resistant fire resisting compliant conductive paper is high, therefore it is expected to be used for electric heater neck
Domain.
Embodiment 6：The water stability of hydroxyapatite overlong nanowire waterproof heat-resisting fire resisting compliant conductive paper
After waterproof heat-resisting fire resisting compliant conductive paper prepared by embodiment 3 is linked to be circuit with ammeter and dc source (3V),
Waterproof heat-resisting fire resisting compliant conductive paper is immersed in water, the real-time electricity that record passes through waterproof heat-resisting fire resisting compliant conductive paper
Stream.As a result Figure 10 is seen, in water immersion process (120 seconds), electric current steadily rises, and amplitude of variation is little, electric current in whole process
It is only 3.65% to change relative value, shows that waterproof heat-resisting fire resisting compliant conductive paper runs in water and has high stability.Will leaching
After the waterproof heat-resisting fire resisting compliant conductive paper to duck in drink and LED etc. are linked to be circuit, in 120 seconds, LED can normally be sent out
Go out light, as shown in figure 11.
Embodiment 7：The fire resistance of hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper
, will be resistance to after high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3 is linked to be circuit with ammeter and dc source (3V)
High-temperature flame-proof compliant conductive paper is placed on calcination in fire, the real-time current that record passes through high temperature resistant fire resisting compliant conductive paper.Experiment knot
As shown in Figure 12, during calcination (420 seconds), incipient stage electric current rises comparatively fast fruit, then tends to be steady, in whole process
Largest current change relative value is 15.35%.After calcination terminates, the electrical property of high temperature resistant fire resisting compliant conductive paper is maintained at
90.6%, show that high temperature resistant fire resisting compliant conductive paper runs in fire and has high stability.The high temperature resistant of calcination in fire will be placed on
After fire resisting compliant conductive paper and LED etc. are linked to be circuit, in 420 seconds, LED can keep normal operation, as shown in figure 13.
Embodiment 8：The anti-icing and deicing performance of hydroxyapatite overlong nanowire high temperature resistant fire resisting compliant conductive paper
Copper foil is wrapped up in the both sides of the high temperature resistant fire resisting compliant conductive paper prepared by embodiment 3, passes through wire and dc source phase
Even, ice cube is placed on high temperature resistant fire resisting compliant conductive paper, the output voltage for adjusting DC voltage is 20V, high temperature resistant fire resisting
The temperature of compliant conductive paper added to more than 200 DEG C in sharp increase of having to go to the toilet in 10 seconds, and high temperature makes ice cube be melted into water, and because resistance to height rapidly
Warm fire resisting compliant conductive paper has water resistance and ultra-hydrophobicity, and the water electrode of thawing is easily from high temperature resistant fire resisting compliant conductive paper table
Face freely tumbles, and whole ice detachment is as shown in figure 14.
Embodiment 9：The preparation of hydroxyapatite overlong nanowire super hydrophobic high temperature fire resisting compliant conductive paper
Conductive filler-conductive black used, as shown in Figure 2.The ethanol solution of the conductive black containing 5mg and the phosphorus of hydroxyl containing 45mg
The ethanol solution mixing of lime stone overlong nanowire, magnetic agitation are filtered after 10 minutes and remove ethanol, and 5 are dried on 90 DEG C of hot plates
Minute, water contact angle is 0 °.High temperature resistant fire resisting compliant conductive paper is placed in dimethyl silicone polymer dilution and soaks 30 points
Clock.The mass ratio of dimethyl silicone polymer dilution is：Dimethyl silicone polymer: curing agent: ethyl acetate=10: 1: 100.
After immersion terminates, it is small that the high temperature resistant fire resisting compliant conductive paper for being coated with dimethyl silicone polymer is placed on solidification 1 at 100 DEG C
When, it is~94 microns of waterproof heat-resisting fire resisting compliant conductive paper to obtain thickness.Prepared waterproof heat-resisting is resistance in this embodiment
The electrical conductivity of fiery compliant conductive paper is 5.7S/m, and water contact angle is~151 °.
Embodiment 10：The preparation of hydroxyapatite overlong nanowire super hydrophobic high temperature fire resisting compliant conductive paper
Conductive filler used-conductive copper particle (particle diameter is 100 nanometers~1 micron).The ethanol of the particle of conductive copper containing 20mg is molten
The ethanol solution of liquid and the overlong nanowire of hydroxyapatite containing 30mg mixes, and magnetic agitation filters after 10 minutes and removes ethanol,
Dried 5 minutes on 90 DEG C of hot plates, water contact angle is 0 °.It is dilute that high temperature resistant fire resisting compliant conductive paper is placed on dimethyl silicone polymer
Release in liquid and soak 30 minutes.The mass ratio of dimethyl silicone polymer dilution is：Dimethyl silicone polymer: curing agent: acetic acid second
Ester=10: 1: 100.After immersion terminates, the high temperature resistant fire resisting compliant conductive paper for being coated with dimethyl silicone polymer is placed on 100
Solidify 1 hour at DEG C, it is~90 microns of waterproof heat-resisting fire resisting compliant conductive paper to obtain thickness.It is prepared in this embodiment to prevent
The electrical conductivity of water high temperature resistant fire resisting compliant conductive paper is about 32S/m, and water contact angle is~150 °.
Industrial applicability：
The invention provides a kind of high temperature resistant fire resisting compliant conductive paper based on hydroxyapatite overlong nanowire and its preparation side
Method, method is simple, and raw material is easy to get, and cost is relatively low, without specific apparatus, easily realizes prepared by mass.Prepared high temperature resistant is resistance to
The electric performance stablity of fiery compliant conductive paper, can normal operation work under highly basic, high humility, hot environment.The present invention also carries
High temperature resistant fire resisting compliant conductive paper has been supplied to be led in waterproof conductive paper, fire resisting conductive paper, high temperature resistant conductive paper, high temperature resistant fire resisting waterproof
Electric paper, waterproof, damp proof protection against the tide, anti-icing and deicing, electric heater, high temperature resistant fire resisting flexible PCB, high temperature resistant fire resisting flexible electronic
Application in the fields such as product.High temperature resistant fire resisting waterproof conductive paper, which is either immersed in water, is also placed on calcination in fire, its electricity
The amplitude of variation of performance is smaller, can guarantee that the normal operation of LED；As electric heater, it is heated high temperature resistant fire resisting conductive paper
Efficiency high, more than 200 DEG C of temperature was can reach in 10 seconds；Excellent electrical heating effect and super hydrophobic surface make high temperature resistant fire resisting
Waterproof conductive paper has good anti-icing and deicing effect.
Claims (9)
- A kind of 1. high temperature resistant fire resisting compliant conductive paper based on hydroxyapatite overlong nanowire, it is characterised in that the resistance to height The composition of warm fire resisting compliant conductive paper includes hydroxyapatite overlong nanowire and conductive filler, and the conductive filler includes conduction Carbon black or/and conducting metal particles, mass percent of the conductive filler in high temperature resistant fire resisting compliant conductive paper be 1~ 70%, preferably 10~40%.
- 2. the high temperature resistant fire resisting compliant conductive paper according to claim 1 based on hydroxyapatite overlong nanowire, it is special Sign is that the high temperature resistant fire resisting compliant conductive paper surface is also coated with dimethyl silicone polymer super-hydrophobic layer, the poly- diformazan The thickness of radical siloxane super-hydrophobic layer is 1~100 micron.
- 3. the high temperature resistant fire resisting compliant conductive paper according to claim 2 based on hydroxyapatite overlong nanowire, it is special Sign is, the high temperature resistant fire resisting compliant conductive paper is positioned in dimethyl silicone polymer dilution and soaked 10~200 minutes Afterwards, solidify 0.1~24 hour at 50~200 DEG C, it is flexible to obtain high temperature resistant fire resisting of the surface coated with dimethyl silicone polymer Conductive paper.
- 4. the high temperature resistant fire resisting compliant conductive paper according to claim 3 based on hydroxyapatite overlong nanowire, it is special Sign is that the mass ratio of dimethyl silicone polymer, curing agent and ethyl acetate is in the dimethyl silicone polymer dilution（5 ~15）∶（0.5~1.5）∶（50~150）, preferably 10: 1: 100.
- 5. the high temperature resistant fire resisting flexibility based on hydroxyapatite overlong nanowire according to any one of claim 1-4 is led Electric paper, it is characterised in that the particle diameter of the conductive filler is 10 nanometers~100 microns, the preferable conducting metal particles Including at least one of Au, Pt, Ag, Cu, Al and Fe.
- 6. the high temperature resistant fire resisting flexibility based on hydroxyapatite overlong nanowire according to any one of claim 1-5 is led Electric paper, it is characterised in that the length of the hydroxyapatite overlong nanowire is 20~2000 microns, a diameter of 5~100 receive Rice.
- 7. the high temperature resistant fire resisting flexibility based on hydroxyapatite overlong nanowire according to any one of claim 1-6 is led Electric paper, it is characterised in that the thickness of the high temperature resistant fire resisting compliant conductive paper is 10~3000 microns.
- It is 8. a kind of soft including the high temperature resistant fire resisting based on hydroxyapatite overlong nanowire any one of claim 1-7 The electric heater of property conductive paper.
- 9. a kind of high temperature resistant fire resisting based on hydroxyapatite overlong nanowire as any one of claim 1-7 is flexible Conductive paper is soft in waterproof, fire resisting, high temperature resistant, damp proof protection against the tide, anti-icing and deicing, high temperature resistant fire resisting flexible PCB, high temperature resistant fire resisting Application in property electronic device.
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| CN115093239A (en) * | 2022-06-05 | 2022-09-23 | 西北工业大学 | Paper with hydrophobic and fireproof properties and preparation method thereof |
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Application publication date: 20171215 |