CN102749314A - Visualization of fingerprints on skin with Fe3O4/SiO2@ Gd2O3: eu, bi material - Google Patents

Visualization of fingerprints on skin with Fe3O4/SiO2@ Gd2O3: eu, bi material Download PDF

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CN102749314A
CN102749314A CN2012102403671A CN201210240367A CN102749314A CN 102749314 A CN102749314 A CN 102749314A CN 2012102403671 A CN2012102403671 A CN 2012102403671A CN 201210240367 A CN201210240367 A CN 201210240367A CN 102749314 A CN102749314 A CN 102749314A
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fingerprint
sio
magnetic
skin
nano material
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CN102749314B (en
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吕家根
刘娜
鲁芳
朱依娜
聂迎春
汪永丽
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Shaanxi Normal University
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Shaanxi Normal University
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Abstract

The invention provides a method for developing fingerprint on skin by using Fe3O4/SiO2@Gd2O3:Eu,Bi materials. The method comprises the following steps: utilizing both good magnetism and strong fluorescence properties of Fe3O4/SiO2@Gd2O3:Eu,Bi magnetic-fluorescence nano materials of a core-shell structure, brushing on a fingerprint which is transferred on the surface of a glass sheet, by a fingerprint brush tip, combining the fingerprint, and developing the fingerprint texture under irradiation of ultraviolet light. The method can be used for overcoming the defect that the magnetic powder method has low sensitivity of developing the fingerprint on the skin, improves the developing success rate of the fingerprint on the skin, is clear for the developed fingerprint on the skin, obvious for contours; and the developing method is simple, and easy to implement, and the Fe3O4/SiO2@Gd2O3:Eu,Bi magnetic-fluorescence nano materials have stable properties, are easy to store, consumes less, and can be used for greatly improving the developing efficiency of the fingerprint on the skin.

Description

Use Fe 3O 4/ SiO 2Gd 2O 3: Eu, the Bi material manifests the method for fingerprint on the skin
Technical field
The invention belongs to the fingerprint detection technical field, be specifically related to be used to manifest the development of fingerprint that comprises on the multiple matrix such as skin, wall brick.
Background technology
Fingerprint is human distinctive skin streakline form.It is typical inhereditary feature, has variant, the unchangeable characteristic of people.In science and technology concerning criminal matters, fingerprint identification is the important means in order to personal individual identification, and fingerprint also once once was considered to " first of the evidence ".Along with the development of dna technique, also normal in the judicial expertise in recent years with the important means of dna technique as the material evidence evaluation.In some cases; Be no lack of with the case of DNA survey report, even have the people to think that dna technique can replace fingerprint technique in material evidence is identified as unique judgment basis, but because defectives such as the acquired difference of DNA sample and pollution; Therefore; In the criminal investigation practice of reality, fingerprint is still the most effective and most important material evidence, receives the great attention of various countries criminal investigation department.
Through years of researches and practice, the fingerprint manifestation technology has obtained significant achievement, and the fingerprint on the most of objects in spot can both obtain comparatively satisfied manifesting, but is still a significant short slab to detecting and manifesting of laten fingerprints on the human body skin.Need from criminal investigation; Residual laten fingerprints on pernicious especially homicide case victim skin; Importance to scene reconstruction and suspect's identity authentication is immeasurable, and the laten fingerprints on these skins often also is an availability fingerprint material evidence unique in this type of case.To detect, manifest the main cause of difficulty be that sweat gland and sebaceous glands on the skin can constantly secrete sweat and sebum liquid to laten fingerprints on the skin, causes the union dyeing to fingerprint residues material on the skin.Discover that skin surface has the fingerprint residues zone and the sweat concentration of no fingerprint residual region to exist evident difference, this is because palm pore density far above other position, the whole body, it is generally acknowledged that their density ratio can reach 4:1～5:1.If can in time effectively dispose live body or corpse Suspected Area skin, the laten fingerprints that manifests on the skin is possible.Through Chinese scholars years of researches and exploration, people attempt adopting iodine to smoke the silver plate transfer printing, Magnaglo method, 502 is smoked several different methods such as showing methods, fluorescence method and manifested the fingerprint on the human body skin.When wherein adopting the Magnaglo method, the Magnaglo that does not combine with the fingerprint lines can be removed under the effect of externally-applied magnetic field, so the background interference of this method is little, the fingerprint recognition ability is strong; But because the signal sensitivity of Magnaglo method is low, so its success ratio that manifests fingerprint on the skin is not high.When adopting fluorescence method, high signal identification sensitivity is its maximum advantage, but because background interference is serious, and the fingerprint manifestation success ratio is not high, in real work, is difficult to use.
Summary of the invention
The objective of the invention is to overcome low, the unclear problem of lines of fingerprint manifestation success ratio on the skin of the prior art, a kind of Fe of utilization is provided 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material manifests the method for fingerprint on the skin.
The technical scheme of technical solution problem of the present invention is: use Fe 3O 4/ SiO 2Gd 2O 3: Eu, the Bi material manifests the method for fingerprint on the skin, is specially:
1) fingerprint transfer printing
By being pressed on the dermal matrix that leaves fingerprint, glass sheet fully contacts 3～5s with matrix, and the fingerprint on the dermal matrix is transferred on the glass sheet, takes off glass sheet with transparent glass sheet;
2) utilize Fe 3O 4/ SiO 2Gd 2O 3: Eu, the magnetic flourescent nano material for magnetic of Bi manifests fingerprint
With fingerprint brush point contact Fe 3O 4/ SiO 2Gd 2O 3: Eu, the Bi magnetic flourescent nano material for magnetic, the shake brush holder makes Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic flourescent nano material for magnetic drop on the glass sheet that leaves fingerprint, and be moving along fingerprint lines brush, removes the Fe that does not combine with fingerprint with magnet 3O 4/ SiO 2Gd 2O 3: Eu, the Bi magnetic flourescent nano material for magnetic will be combined with Fe 3O 4/ SiO 2Gd 2O 3: Eu, the glass sheet of Bi magnetic flourescent nano material for magnetic place to excite under the ultraviolet source and show fingerprint, observe or take the record fingerprint.
Above-mentioned Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material is processed by following method:
A) remove ionized water and join in the there-necked flask and to stir logical argon gas deoxygenation 30 minutes, take by weighing FeCl 36H 2O and FeSO 47H 2O is that 1:1.8～2.0 join in the there-necked flask according to mass ratio, stirs accelerate dissolution, 500 rev/mins of stirring rates, and obtaining the solution solid-to-liquid ratio is 0.082g/mL, heat temperature raising to 60 ℃; Add strong aqua, the pH of regulator solution is 9～10, stirring reaction 30 minutes, and temperature of reaction is elevated to 80 ℃; Ageing 30 minutes is cooled to room temperature, and magnet separates, deionized water wash three times; Absolute ethanol washing three times, vacuum drying was dried 6 hours, and was obtained Fe for 50～60 ℃ 3O 4Magnetic nano-particle;
B) take by weighing Fe in the step a) 3O 4It is 50% ethanol water that magnetic nano-particle places volumetric concentration, ultrasonic dispersion, and obtaining the solution solid-to-liquid ratio is 0.012g/mL, rotating speed is 350 rev/mins; Stirred 30 minutes, and added ethyl orthosilicate, the volume ratio of ethyl orthosilicate and ethanol water is 1:45～55, and rotating speed is 350 rev/mins; Stirred 30 minutes, and added ammoniacal liquor, the volume ratio of ethanol water and ammoniacal liquor is 1:20; Stirring reaction is 2 hours under the room temperature, and magnet separates, deionized water wash three times; Absolute ethanol washing three times places the interior 50 ℃ of oven dry of vacuum drying chamber 6 hours, obtains Fe 3O 4/ SiO 2Composite nanoparticle;
C) with the Fe of step b) 3O 4/ SiO 2Composite nanoparticle is that mix 1:6～10 with cetyl trimethyl ammonium bromide by mass ratio, joins volumetric concentration and is in 50% the ethanol water, and obtaining the solution solid-to-liquid ratio is 0.025g/mL; Ultrasonic dispersion, stirring at room 2 hours, rotating speed is 350 rev/mins; The magnet separation obtains deposit; Deposit is respectively washed 3 times vacuum drying, the Fe that obtains modifying with deionized water and absolute ethyl alcohol 3O 4/ SiO 2Composite nanoparticle;
D) take by weighing the Fe that step c) is modified 3O 4/ SiO 2Composite nanoparticle adds in the entry, ultrasonic dispersion, and obtaining the solution solid-to-liquid ratio is 0.002g/mL, adds gadolinium nitrate solution, europium nitrate solution and bismuth nitrate solution, the Fe after the modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:6～11:0.1～1:0.1～1, ultrasonic 5 minutes, and 75 ℃ of mechanical raking; Rotating speed is 350 rev/mins; Dripping concentration is the urea liquid of 0.03g/mL, and dripping speed is 5mL/min, the Fe of modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and urea is 1:30, and constant temperature 0.5 hour changes the gained mixed liquor over to agitated reactor; 188 ~ 192 ℃ were reacted 17 ~ 19 hours in muffle furnace, were cooled to room temperature, with precipitate with deionized water in the agitated reactor and absolute ethanol washing; Clarify up to cleansing solution, the deposition after the washing is placed in the vacuum drying chamber dried 6 hours about 50 ℃, change in the porcelain boat; Under the nitrogen atmosphere protection, place 500～800 ℃ of high-temperature calcinations of tubular furnace 8 hours, obtain Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material.
Above-mentioned steps d) Fe after modifying in 3O 4/ SiO 2Composite nanoparticle and gadolinium nitrate, europium nitrate, the preferable mass ratio of bismuth nitrate are 1:9～10:0.3～0.6:0.3～0.6.
Above-mentioned steps is middle FeCl a) 36H 2O and FeSO 47H 2The preferable mass ratio of O is 1:1.9.
The present invention uses Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi material manifest that the method for fingerprint is to utilize the Fe of nucleocapsid structure on the skin 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material have magnetic and two kinds of functions of fluorescence, have good magnetic and strong photoluminescent property simultaneously; With fingerprint brush point its brush is attached on the fingerprint that is transferred to glass sheet surface, combines, under ultraviolet excitation, manifest the fingerprint lines with fingerprint; It has remedied the lower deficiency of fingerprint sensitivity on the existing skin of Magnaglo Faxian, has improved the success ratio of fingerprint manifestation on the skin, and the fingerprint texture that manifests on the skin is clear; Profile is clear; Process for show of the present invention is simple, and is easy to implement, the Fe that utilizes CTAB to modify among the present invention 3O 4/ SiO 2Composite nanoparticle is nuclear, and rare-earth luminescent material is the shell material, is prepared into the Fe of nucleocapsid structure 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material, its stable in properties is easy to preserve, and consumption is less, has improved the efficient of fingerprint manifestation on the skin greatly.
Description of drawings
Fig. 1 is for to manifest the fingerprint image that is transferred on the glass sheet with magnetic-fluorescent nano material.
Fig. 2 is for manifesting the image of fingerprint on the skin in the Comparative Examples.
Embodiment
Combine accompanying drawing and embodiment to the Fe of using of the present invention at present 3O 4/ SiO 2Gd 2O 3: Eu, Bi material manifest that the method for fingerprint further specifies on the skin, but the present invention is not limited only to following embodiment.
Embodiment 1
Present embodiment utilizes Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material manifests the method for fingerprint on the skin, includes following steps:
Step 1: fingerprint transfer printing
By being pressed on the human body skin that leaves fingerprint, glass sheet fully contacts 3～5s with skin, and the fingerprint on the skin is transferred on the glass sheet, takes off glass sheet with transparent glass sheet;
Step 2: utilize Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material manifests fingerprint
The glass sheet that will be printed on fingerprint is placed on the table, clings four jiaos with adhesive tape, with fingerprint brush point contact Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material rotates brush holder 3 times with thumb and forefinger, makes fingerprint brush point adhere to an amount of powder, mentions the fingerprint brush slightly, rotates brush holder again 3 times, and to remove too much powder on the brush, the shake brush holder makes Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material drop on the glass sheet that leaves fingerprint, and be moving along fingerprint lines brush, makes Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material fully combines with the fingerprint residues material, removes the Fe that does not combine with fingerprint with magnet 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material will be combined with Fe 3O 4/ SiO 2Gd 2O 3: Eu, the glass sheet of Bi magnetic-fluorescent nano material places under the ultraviolet source 253.7nm and excites, and takes fingerprint image with Nikon D3000 type digital camera, shows fingerprint on glass, referring to Fig. 1.
Above-mentioned Fe 3O 4/ SiO 2Gd 2O 3: Eu, the preparation method of Bi magnetic-fluorescent nano material comprises the steps:
Step a: get and stir logical argon gas deoxygenation 30 minutes in the there-necked flask that the 60mL deionized water joins 150mL, take by weighing 1.71g FeCl 36H 2O and 3.24g FeSO 47H 2O is that 1:1.9 joins in the there-necked flask according to mass ratio, mechanical raking, and 500 rev/mins of stirring rates, accelerate dissolution obtains the FeCl of mixed liquor 36H 2O and FeSO 47H 2The solid-to-liquid ratio that O and deionized water form is 0.082g/mL, and heat temperature raising to 60 ℃ adds the strong aqua of 8mL, and the pH of regulator solution is 9.5; Stirring reaction 30 minutes, temperature of reaction are elevated to 80 ℃, ageing 30 minutes; Naturally cool to room temperature, magnet separates the material obtain, with deionized water wash three times; With absolute ethanol washing three times, place inherent about 50～60 ℃ oven dry of vacuum drying chamber 6 hours, obtain Fe 3O 4Magnetic nano-particle;
Step b: take by weighing the 0.174g Fe among the step a 3O 4Magnetic nano-particle places 50% ethanol water, ultrasonic dispersion 10 minutes, and obtaining the solution solid-to-liquid ratio is 0.012g/mL, rotating speed is 350 rev/mins; Stirred 30 minutes, and added ethyl orthosilicate, the volume ratio of ethyl orthosilicate and ethanol water is 1:50, and rotating speed is 350 rev/mins; Stirred 30 minutes, and added the 0.75mL strong aqua, make that the volume ratio of ethanol water and ammoniacal liquor is 1:20; Stirring reaction is 2 hours under the room temperature, and magnet separates the material obtain, with deionized water wash three times; Absolute ethanol washing three times places the interior 50 ℃ of oven dry of vacuum drying chamber 6 hours, obtains Fe 3O 4/ SiO 2Composite nanoparticle;
Step c: get the Fe among the 0.5615g step b 3O 4/ SiO 2Composite nanoparticle mixes Fe with the 4.492g cetyl trimethyl ammonium bromide 3O 4/ SiO 2The mass ratio of composite nanoparticle and cetyl trimethyl ammonium bromide is 1:8, adds in the absolute ethyl alcohol WS, and obtaining the solution solid-to-liquid ratio is 0.025g/mL; Ultrasonic dispersion 5 minutes, stirring at room 2 hours, rotating speed is 350 rev/mins; The magnet separation obtains the pitchy deposit; The pitchy deposit is respectively washed 3 times with deionized water and absolute ethyl alcohol, placed the interior 60 ℃ of following dryings of vacuum drying chamber 6 hours, the Fe that obtains modifying 3O 4/ SiO 2Composite nanoparticle;
Steps d: take by weighing the Fe that modifies among the step c 3O 4/ SiO 2Composite nanoparticle 0.1176g adds in the 50mL water, ultrasonic dispersion 5 minutes, and obtaining the solution solid-to-liquid ratio is 0.002g/mL, adds 25mL gadolinium nitrate solution, 2.75mL europium nitrate solution and 2.75mL bismuth nitrate solution, the Fe of modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:9.5:0.5:0.5, changes in the 250mL three-neck flask 75 ℃ of mechanical raking after ultrasonic 5 minutes over to; Rotating speed is 350 rev/mins; Dripping concentration is the urea liquid of 0.03g/mL, drips fast control bit 5mL/min, the Fe of modification 3O 4/ SiO 2Composite nanoparticle is 1:30 with the urea quality ratio, and constant temperature 0.5 hour changes the gained mixed liquor over to agitated reactor; In muffle furnace, reacted 18 hours under 190 ℃ of conditions, be cooled to room temperature, the reddish-brown precipitation in the agitated reactor is used deionized water and absolute ethanol washing respectively; Clarify up to cleansing solution, the reddish-brown precipitation after the washing is placed in the vacuum drying chamber dried 6 hours about 50 ℃, change in the porcelain boat; Under the nitrogen atmosphere protection, place 700 ℃ of high-temperature calcinations of tubular furnace 8 hours, obtain Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material.
Embodiment 2
The Fe that utilizes at the foregoing description 1 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material manifest in the method for fingerprint on the skin, the Fe in the step 2 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material is processed by following steps:
Step a: get and stir logical argon gas deoxygenation 30 minutes in the there-necked flask that the 61.5mL deionized water joins 150mL, take by weighing 1.80g FeCl 36H 2O and 3.24g FeSO 47H 2O is that 1:1.8 joins in the there-necked flask according to mol ratio, mechanical raking, 500 rev/mins of stirring rates; Accelerate dissolution, obtaining the solution solid-to-liquid ratio is 0.082g/mL, heat temperature raising to 60 ℃; The strong aqua that adds 6mL; The pH of regulator solution is 9, and other the operation of this step is identical with embodiment 1, obtains Fe 3O 4Magnetic nano-particle;
Step b: take by weighing the 0.174g Fe among the step a 3O 4It is 50% ethanol water that magnetic nano-particle places volumetric concentration, ultrasonic dispersion 10 minutes, and obtaining the solution solid-to-liquid ratio is 0.012g/mL; Rotating speed is 350 rev/mins, stirs 30 minutes, adds the 0.375mL ethyl orthosilicate; The volume ratio of ethyl orthosilicate and ethanol water is 1:40, and rotating speed is 350 rev/mins, stirs 30 minutes; Add the 0.75mL strong aqua, other the operation of this step is identical with embodiment 1, obtains Fe 3O 4/ SiO 2Composite nanoparticle;
Step c: get Fe among the 0.5615g step b 3O 4/ SiO 2Composite nanoparticle mixes Fe with the 3.369g cetyl trimethyl ammonium bromide 3O 4/ SiO 2The mass ratio of composite nanoparticle and cetyl trimethyl ammonium bromide is 1:6, join in 50% the ethanol water, in this step other operation identical with embodiment 1, the Fe after obtaining modifying 3O 4/ SiO 2Composite nanoparticle;
Steps d: take by weighing the Fe that modifies among the step c 3O 4/ SiO 2Composite nanoparticle 0.1176g adds in the 50mL water, ultrasonic dispersion 5 minutes, and obtaining the solution solid-to-liquid ratio is 0.002g/mL, adds 23.7mL gadolinium nitrate solution, 1.65mL europium nitrate solution and 1.65mL bismuth nitrate solution, the Fe after the modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:9:0.3:0.3, changes in the 250mL three-neck flask 75 ℃ of mechanical raking after ultrasonic 5 minutes over to; Rotating speed is 350 rev/mins; Dripping concentration is the urea liquid of 0.03g/mL, drips speed control and is made as 5mL/min, the Fe of modification 3O 4/ SiO 2Composite nanoparticle is 1:30 with the urea quality ratio, constant temperature 0.5 hour, and other operation in this step is identical with embodiment 1, obtains Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material.
Other step is identical with embodiment 1.
Embodiment 3
The Fe that utilizes at the foregoing description 1 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material manifest in the method for fingerprint on the skin, the Fe in the step 2 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material is processed by following steps:
Step a: get and stir logical argon gas deoxygenation 30 minutes in the there-necked flask that the 59mL deionized water joins 150mL, take by weighing 1.62g FeCl 36H 2O and 3.24g FeSO47H 2O is that 1:2 joins in the there-necked flask according to mass ratio, mechanical raking, 500 rev/mins of stirring rates; Accelerate dissolution, obtaining the solution solid-to-liquid ratio is 0.082g/mL, heat temperature raising to 60 ℃; The strong aqua that adds 9mL; The pH of regulator solution is 10, and other the operation of this step is identical with embodiment 1, obtains Fe 3O 4Magnetic nano-particle;
Step b: take by weighing the 0.174g Fe among the step a 3O 4It is 50% ethanolic solution that magnetic nano-particle places volumetric concentration, and ultrasonic dispersion 10 minutes obtains the Fe that concentration is 0.012g/mL 3O 4Magnetic nano-particle ethanolic solution, rotating speed are 350 rev/mins, stir 30 minutes; Add the ethyl orthosilicate of 0.33mL, the volume ratio of ethyl orthosilicate and ethanol water is 1:55, and rotating speed is 350 rev/mins; Stirred 30 minutes; Add 0.75mL ammoniacal liquor, other the operation of this step is identical with embodiment 1, obtains Fe 3O 4/ SiO 2Composite nanoparticle;
Step c: get Fe among the 0.5615g step b 3O 4/ SiO 2Composite nanoparticle mixes Fe with the 5.615g cetyl trimethyl ammonium bromide 3O 4/ SiO 2The mass ratio of composite nanoparticle and cetyl trimethyl ammonium bromide is 1:10, add in 50% the ethanol water, in this step other operation identical with embodiment 1, the Fe that obtains modifying 3O 4/ SiO 2Composite nanoparticle;
Steps d: take by weighing the Fe that modifies among the step c 3O 4/ SiO 2Composite nanoparticle 0.1176g adds in the 50mL water, ultrasonic dispersion 5 minutes, and obtaining the solution solid-to-liquid ratio is 0.002g/mL, adds 26.4mL gadolinium nitrate solution, 3.3mL europium nitrate solution and 3.3mL bismuth nitrate solution, the Fe after the modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:10:0.6:0.6, changes in the 250mL three-neck flask 75 ℃ of mechanical raking after ultrasonic 5 minutes over to; Rotating speed is 350 rev/mins; Dripping concentration is the urea liquid of 0.03g/mL, drips a speed control and is made as 5mL/min, makes Fe in the solution 3O 4/ SiO 2Composite nanoparticle is 1:30 with the urea quality ratio, constant temperature 0.5 hour, and other operation in this step is identical with embodiment 1, obtains Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material.
Other step is identical with embodiment 1.
Embodiment 4
The foregoing description 1 ~ 3 utilize Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano particles manifests the method for fingerprint on the skin, at preparation Fe 3O 4/ SiO 2Gd 2O 3: Eu, steps d takes by weighing the Fe of modification in the method for Bi magnetic-fluorescent nano material 3O 4/ SiO 2Composite nanoparticle 0.1176g adds in the 50mL water, ultrasonic dispersion 5 minutes, and obtaining the solution solid-to-liquid ratio is 0.002g/mL, adds 15.84mL gadolinium nitrate solution, 0.55mL europium nitrate solution and 0.55mL bismuth nitrate solution, the Fe of modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:6:0.1:0.1, and other operation is identical with respective embodiments in this step.
Other step is identical with respective embodiments.
Embodiment 5
The foregoing description 1 ~ 3 utilize Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano particles manifest in the method for fingerprint on the skin, at preparation Fe 3O 4/ SiO 2Gd 2O 3: Eu, steps d takes by weighing the Fe after the modification in the method for magnetic-fluorescent nano material of Bi 3O 4/ SiO 2Composite nanoparticle 0.1176g adds in the 50mL water, ultrasonic dispersion 5 minutes, and obtaining the solution solid-to-liquid ratio is 0.002g/mL, adds 29.04mL and divides gadolinium nitrate solution, 6.05mL europium nitrate solution and 6.05mL bismuth nitrate solution, the Fe after the modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:11:1:1, and other operation is identical with respective embodiments in this step.
Other step is identical with respective embodiments.
Embodiment 6
The foregoing description 1 ~ 5 utilize Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material manifest in the method for fingerprint on the skin, at preparation Fe 3O 4/ SiO 2Gd 2O 3: Eu, the Fe after modifying in the steps d in the method for Bi magnetic-fluorescent nano material 3O 4/ SiO 2Composite nanoparticle adds in the entry, and ultrasonic dispersion adds gadolinium nitrate solution, europium nitrate solution and bismuth nitrate solution; Ultrasonic 5 minutes, 75 ℃ of mechanical raking, rotating speed is 350 rev/mins; Dripping concentration is the urea liquid of 0.03g/mL, changes the gained mixed liquor over to agitated reactor, and 188 ℃ were reacted 19 hours in muffle furnace; Be cooled to room temperature, the reddish-brown precipitation in the agitated reactor with deionized water and absolute ethanol washing, is clarified up to cleansing solution; Reddish-brown precipitation after the washing is placed in the vacuum drying chamber about 50 ℃ oven dry 6 hours, change in the porcelain boat, under the nitrogen atmosphere protection, place 500 ℃ of high-temperature calcinations of tubular furnace 8 hours; Other step is identical with respective embodiments, obtains Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material.
Other step is identical with respective embodiments.
Embodiment 7
The foregoing description 1 ~ 5 utilize Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material manifests the method for fingerprint on the skin, at preparation Fe 3O 4/ SiO 2Gd 2O 3: Eu, the Fe after steps d is modified in the method for magnetic-fluorescent nano material of Bi 3O 4/ SiO 2Composite nanoparticle adds in the entry, and ultrasonic dispersion adds gadolinium nitrate solution, europium nitrate solution and bismuth nitrate solution; Ultrasonic 5 minutes, 75 ℃ of mechanical raking, rotating speed is 350 rev/mins; Dripping concentration is the urea liquid of 0.03g/mL, changes the gained mixed liquor over to agitated reactor, and 192 ℃ were reacted 17 hours in muffle furnace; Be cooled to room temperature,, clarify up to cleansing solution with precipitate with deionized water in the agitated reactor and absolute ethanol washing; Reddish-brown precipitation after the washing is placed in the vacuum drying chamber about 50 ℃ oven dry 6 hours, change in the porcelain boat, under the nitrogen atmosphere protection, place 800 ℃ of high-temperature calcinations of tubular furnace 8 hours; Other step is identical with respective embodiments, obtains Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material.
Other step is identical with respective embodiments.
In order to prove beneficial effect of the present invention, the fingerprint that fingerprint that the embodiment of the invention 1 is manifested and following Comparative Examples are manifested compares, and is specific as follows:
Comparative Examples is on skin, to restrain same fingerprint, directly with fingerprint brush point contact Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material, the shake brush holder makes Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material drop on the glass sheet that leaves fingerprint, and be moving along fingerprint lines brush, makes Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material fully combines with the fingerprint residues material, removes the Fe that does not combine with fingerprint with magnet 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material will be combined with Fe 3O 4/ SiO 2Gd 2O 3: Eu, the glass sheet of Bi magnetic-fluorescent nano material places under the uviol lamp and excites under the 253.7nm, takes fingerprint image with Nikon D3000 type digital camera, shows the fingerprint on the skin, and is as shown in Figure 2.
By Fig. 1 and Fig. 2 contrast, can directly draw, the fingerprint profile on the skin that the inventive method manifests is clear, and lines is more clear, can fingerprint be displayed truly.

Claims (4)

1. use Fe for one kind 3O 4/ SiO 2Gd 2O 3: Eu, the Bi material manifests the method for fingerprint on the skin, it is characterized in that said method is:
1) fingerprint transfer printing
By being pressed on the dermal matrix that leaves fingerprint, glass sheet fully contacts 3～5s with matrix, and the fingerprint on the dermal matrix is transferred on the glass sheet, takes off glass sheet with transparent glass sheet;
2) utilize Fe 3O 4/ SiO 2Gd 2O 3: Eu, the magnetic flourescent nano material for magnetic of Bi manifests fingerprint
With fingerprint brush point contact Fe 3O 4/ SiO 2Gd 2O 3: Eu, the Bi magnetic flourescent nano material for magnetic, the shake brush holder makes Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic flourescent nano material for magnetic drop on the glass sheet that leaves fingerprint, and be moving along fingerprint lines brush, removes the Fe that does not combine with fingerprint with magnet 3O 4/ SiO 2Gd 2O 3: Eu, the Bi magnetic flourescent nano material for magnetic will be combined with Fe 3O 4/ SiO 2Gd 2O 3: Eu, the glass sheet of Bi magnetic flourescent nano material for magnetic place to excite under the ultraviolet source and show fingerprint, observe or take the record fingerprint.
2. the Fe that uses according to claim 1 3O 4/ SiO 2Gd 2O 3: Eu, the Bi material manifests the method for fingerprint on the skin, it is characterized in that: said Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material is processed by following method:
A) remove ionized water and join in the there-necked flask and to stir logical argon gas deoxygenation 30 minutes, take by weighing FeCl 36H 2O and FeSO 47H 2O is that 1:1.8～2.0 join in the there-necked flask according to mass ratio, stirs accelerate dissolution, 500 rev/mins of stirring rates, and obtaining the solution solid-to-liquid ratio is 0.082g/mL, heat temperature raising to 60 ℃; Add strong aqua, the pH of regulator solution is 9～10, stirring reaction 30 minutes, and temperature of reaction is elevated to 80 ℃; Ageing 30 minutes is cooled to room temperature, and magnet separates, deionized water wash three times; Absolute ethanol washing three times, vacuum drying was dried 6 hours, and was obtained Fe for 50～60 ℃ 3O 4Magnetic nano-particle;
B) take by weighing Fe in the step a) 3O 4It is 50% ethanol water that magnetic nano-particle places volumetric concentration, ultrasonic dispersion, and obtaining the solution solid-to-liquid ratio is 0.012g/mL, rotating speed is 350 rev/mins; Stirred 30 minutes, and added ethyl orthosilicate, the volume ratio of ethyl orthosilicate and ethanol water is 1:45～55, and rotating speed is 350 rev/mins; Stirred 30 minutes, and added ammoniacal liquor, the volume ratio of ethanol water and ammoniacal liquor is 1:20; Stirring reaction is 2 hours under the room temperature, and magnet separates, deionized water wash three times; Absolute ethanol washing three times places the interior 50 ℃ of oven dry of vacuum drying chamber 6 hours, obtains Fe 3O 4/ SiO 2Composite nanoparticle;
C) with the Fe of step b) 3O 4/ SiO 2Composite nanoparticle is that mix 1:6～10 with cetyl trimethyl ammonium bromide by mass ratio, joins volumetric concentration and is in 50% the ethanol water, and obtaining the solution solid-to-liquid ratio is 0.025g/mL; Ultrasonic dispersion, stirring at room 2 hours, rotating speed is 350 rev/mins; The magnet separation obtains deposit; Deposit is respectively washed 3 times vacuum drying, the Fe that obtains modifying with deionized water and absolute ethyl alcohol 3O 4/ SiO 2Composite nanoparticle;
D) take by weighing the Fe that step c) is modified 3O 4/ SiO 2Composite nanoparticle adds in the entry, ultrasonic dispersion, and obtaining the solution solid-to-liquid ratio is 0.002g/mL, adds gadolinium nitrate solution, europium nitrate solution and bismuth nitrate solution, the Fe after the modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:6～11:0.1～1:0.1～1, ultrasonic 5 minutes, and 75 ℃ of mechanical raking; Rotating speed is 350 rev/mins; Dripping concentration is the urea liquid of 0.03g/mL, and dripping speed is 5mL/min, the Fe of modification 3O 4/ SiO 2The mass ratio of composite nanoparticle and urea is 1:30, and constant temperature 0.5 hour changes the gained mixed liquor over to agitated reactor; 188 ~ 192 ℃ were reacted 17 ~ 19 hours in muffle furnace, were cooled to room temperature, with precipitate with deionized water in the agitated reactor and absolute ethanol washing; Clarify up to cleansing solution, the deposition after the washing is placed in the vacuum drying chamber dried 6 hours about 50 ℃, change in the porcelain boat; Under the nitrogen atmosphere protection, place 500～800 ℃ of high-temperature calcinations of tubular furnace 8 hours, obtain Fe 3O 4/ SiO 2Gd 2O 3: Eu, Bi magnetic-fluorescent nano material.
3. the Fe that uses according to claim 2 3O 4/ SiO 2Gd 2O 3: Eu, the Bi material manifests the method for fingerprint on the skin, it is characterized in that: the Fe after modifying in the said step d) 3O 4/ SiO 2The mass ratio of composite nanoparticle and gadolinium nitrate, europium nitrate, bismuth nitrate is 1:9～10:0.3～0.6:0.3～0.6.
4. the Fe that uses according to claim 2 3O 4/ SiO 2Gd 2O 3: Eu, the Bi material manifests the method for fingerprint on the skin, it is characterized in that: FeCl in the said step a) 36H 2O and FeSO 47H 2The mass ratio of O is 1:1.9.
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