CN103611928B - A kind of silver and silver composite nano particles and laser controlling synthetic method thereof - Google Patents
A kind of silver and silver composite nano particles and laser controlling synthetic method thereof Download PDFInfo
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Abstract
The invention belongs to field of material technology, particularly a kind of silver and silver composite nano particles and laser controlling synthetic method thereof.Nano silver grain of the present invention, shape is spherical or elliposoidal, size range 5 ~ 50nm, silver nanoparticle compound particle, chemical composition by weight percentage, by 3 ~ 30wt.%? SiO
2, 70 ~ 97wt.%Ag composition, or by 4 ~ 10wt.%? Ni, 3 ~ 30wt.%? SiO
2, surplus is Ag composition.Synthetic method first prepares target, then control impuls laser device laser Shu Bochang 1064nm, frequency 10-20Hz, laser energy density scope 50-80J/mm
2, irradiation ablation is carried out to target, passes into carrier gas N simultaneously
2, form gas phase forming core and the cluster of argentiferous and compound phase, import in the liquid-phase collection system of temperature 10 ~ 30 DEG C, eventually pass Separation of Solid and Liquid and obtain silver and silver composite nano particles.The present invention environmental protection, disposable synthesis can have single-phase Ag, two-phase Ag-SiO
2, three-phase Ag-Ni-SiO
2and above nano particle, the nano particle of synthesis has that purity is high, the evident characteristic of good dispersion, heterogeneous mixing composite construction and good anti-microbial property and magnetic recovery function.
Description
Technical field
The invention belongs to field of material technology, particularly a kind of silver and silver composite nano particles and laser controlling synthetic method thereof.
Background technology
In order to solve day by day serious germ contamination problem, the corresponding various anti-biotic material that has been born.Wherein silver be nano antibacterial agent become in recent years both at home and abroad primary study and development, one of nano-functional material of polluting a difficult problem can be tackled.Due to the natural disinfectant function of silver (Ag), Nano silver grain can kill 650 various bacteria comprising Escherichia coli in several minutes, having microbe killing properties can strong, the feature such as antibiotic property is lasting and nontoxic, and the fields such as, purification of air, life science antibacterial in catalyst, sterilization have broad application prospects.
But, also there is a difficult problem for following three aspects in the commercial applications of current Nano silver grain: (1) Nano silver grain is unstable, and blackout easy to change under illumination and hot conditions, makes antibacterial lasting effect be deteriorated, and due to the price of silver high, its application cost is also higher; (2) Nano silver grain is easily reunited, and its nano effect is significantly weakened; (3), after sterilization, degradation of contaminant, the separation of the nano particle in liquid to be treated is dispersed in and removal process is complicated and cost is very high.Therefore, the dispersiveness and the stability problem that solve nanoscale Argent grain are one of people's targets studying pursuit always.
Laser method is because having a kind of important method that the features such as synthesizing nano-particle purity is high, particle diameter is little, building-up process is simple are synthesizing nano-particles, and wherein laser Gaseous ablation and liquid phase ablative method have important using value in synthesis silver and silver composite nano particles.That is familiar with Ag nano-complex particle along with people deepens continuously, and the heterogeneous novel antibacterial nano-complex particle that research and design and controlledly synthesis have specific function character has become new primary study direction.Therefore, for reduce that bacterium environmental pollution brings serious harm, development has the low and callable Novel silver nano-complex particle of good anti-microbial property, application cost and Laser synthesizing new technology thereof, not only has important scientific research meaning but also has important using value.
These difficult problems existed in current Nano silver grain application, people mainly have employed the synthetic methods such as chemistry, physics and biology, nanoscale has carried out the scientific research of heterogeneous compound, and has achieved many impressive progresses.Namely by other metal (M), oxide (MO), polymer etc. to Nano silver grain carry out heterogeneous alloy, doping, load and composite modified after, form the novel nano particle that Ag-M, Ag-MO, Ag-M-MO, Polymer-supported Ag etc. have the different composite structures such as alloy, mixed phase, nucleocapsid (clad type), both dispersiveness, the stability of Nano silver grain can have been improved, reduce costs, the character that single-particle does not have can be obtained again, as optics adjustability (Ag-Cu, Ag-Ni, AgSiO
2), optical nonlinearity enhancement effect (Ag-Au, Cu
2oAg), the antibacterial (Ag-TiO of economic benefits and social benefits
2), magnetic give (Ag-Ni, Ag-Fe
3o
4, NiAgTiO
2) etc. character.Therefore, research and development Novel silver nano-complex particle and new synthetic method thereof, solve the many difficult problems existed in the application of Ag nano particle significant.
Summary of the invention
The problems such as the cost existed for Nano silver grain application in prior art is high, poor stability, difficult recovery, the invention provides a kind of silver and silver composite nano particles and laser controlling synthetic method thereof, object controls the key issues such as synthesis around the Composition Design of Novel silver nano particle, functions expanding and laser method, passes through SiO
2, the multicomponent design such as Ni, Ag, constituent adjustment, composite construction regulation and control and magnetic is given and heterogeneous cooperative effect builds, obtain the silver nanoparticle compound particle that pulse laser vapor evaporation-liquid-phase collection controls to synthesize.
A kind of Nano silver grain, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
Silver nanoparticle compound particle of the present invention, its chemical composition by weight percentage, by 3 ~ 30wt.%SiO
2, 70 ~ 97wt.%Ag composition, or by 4 ~ 10wt.%Ni, 3 ~ 30wt.%SiO
2, surplus is Ag composition, and its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of silver of the present invention and silver composite nano particles is carried out according to following steps:
(1) target is prepared:
With Ag powder for raw material, or according to percentage by weight, weigh 3 ~ 30wt.%SiO
2powder, 70 ~ 97wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, or weigh 4 ~ 10wt.%Ni powder, 3 ~ 30wt.%SiO
2powder, surplus is Ag powder, is mixed into Ag-SiO
2-Ni three-phase composite powder, puts into ball grinder and adds ethanol and stir after 0.5 ~ 1h by above-mentioned Ag powder or composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 8 ~ 12h as abrasive material, controls drum's speed of rotation 300 ~ 400 turns/min;
Dry through the Ag powder of ball mill mixing or composite powder, then grind 10 ~ 30min, add binding agent and make cylindrical sample, dry 12h, then at N
2be heated to 600 ~ 700 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target or Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 10-20Hz, laser energy density scope 50-80J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.2-0.5L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 10 ~ 30 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag nano particle, Ag-SiO
2two-phase composite nanoparticle or Ag-Ni-SiO
2three-phase composite nano particle.
Described Ag powder, SiO
2powder and Ni powder are granularities is micron powder.
Described Ag powder or the weight ratio of composite powder and abrasive material are 6:1.
Described binding agent is 504 adhesives.
Described liquid-phase collection system be hold promising volume fraction of ethanol be 10% ~ 50% deionized water or volume fraction be the collection container of 20% ethylene glycol+80% ethanol, the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm is also installed in the middle part of described collection container.
Compared with prior art, feature of the present invention and beneficial effect are:
Process of the present invention utilizes the anti-microbial property of Nano Silver, also by utilizing heterogeneous nano combined heterogeneous synergistic mechanism, plays Ag, Ni, SiO
2each self-applying, be grouped into through the one-tenth of science and be prepared into target, utilize the heterogeneous compound plasma that target is evaporated in high energy laser ablation to produce in the gas phase simultaneously, to reach when closing on nucleation concentration forming core under certain degree of supercooling, then at carrier gas N
2transport under enter fast in liquid-phase collection system and cool fast, condense and be grown to nanometer or nano-complex particle; The surfactant ethylene glycol that liquid-phase collection system clock is appropriate simultaneously carries out original position dispersion, the agglomeration of nano particle can be improved, the temperature of liquid-phase collection system also can be carried out cooling and be controlled, easily small size nano particle is generated in low temperature liquid phase, the stainless (steel) wire of aperture 0.1 ~ 1mm being installed at liquid solution collection container, making bubbles of carrier gas improve synthetic yield by breaking during fine-structure mesh.In sum, in the growth course of liquid phase nanoparticles, by loading the impact of external force factor to liquid-phase system, thus controllably one-step synthesis method has the nano particle of different size, crystal formation, structure; Due to in-situ modification can be carried out to nano-complex particle containing high molecular surfactant in liquid-phase system, define finely disseminated nano particle, reach the object improved and reunite.
The inventive method environmental protection, disposable synthesis can have single-phase, two-phase, three-phase and above novel nano compound particle thereof, and the nano-complex particle of synthesis has that purity is high, the evident characteristic of good dispersion, heterogeneous mixing composite construction and good anti-microbial property and magnetic recovery function.By composition and technical regulation, the predominant size of the nano-complex particle of synthesis is at 5 ~ 50nm, and shape is spherical or elliposoidal; Ag-SiO
2the magnetic of nano-complex particle is weak, along with the increase of compound Ni content, and Ag-Ni-SiO
2the saturation magnetization of Nano Silver compound particle increases gradually, has magnetic recovery function.Antibiotic property analytical proof Ag-Ni-SiO
2novel nano compound particle has good anticolibacillary effect.Novel silver nano-complex particle and the laser controlling synthetic method thereof of the present invention's synthesis have important application prospect.
Accompanying drawing explanation
Fig. 1 is the TEM electron microscopic picture of Ag nano particle prepared by the embodiment of the present invention 1;
Wherein (a) represents resolution ratio is 50nm; B () represents resolution ratio is 20nm;
Fig. 2 is the grain size distribution of Ag nano particle prepared by the embodiment of the present invention 1;
Fig. 3 is the standby Ag-SiO of embodiment of the present invention system 4
2the TEM electron microscopic picture of composite nanoparticle;
Wherein (a) represents resolution ratio is 50nm; B () represents resolution ratio is 20nm;
Fig. 4 is the Ag-SiO that the embodiment of the present invention prepares 4
2the grain size distribution of composite nanoparticle;
Fig. 5 is the Ag nano particle prepared of the embodiment of the present invention 1 and the Ag-SiO for preparing of embodiment 4-10
2the uv-visible absorption spectra figure of composite nanoparticle;
Fig. 6 is Ag-Ni-SiO prepared by embodiment 11
2the TEM electron microscopic picture of composite nanoparticle;
Fig. 7 is Ag-Ni-SiO prepared by embodiment 11
2the grain size distribution of composite nanoparticle;
Fig. 8 is Ag-Ni-SiO prepared by embodiment 11
2the EDS energy spectrogram of composite nanoparticle;
Fig. 9 is Ag-Ni-SiO prepared by embodiment 11
2the XRD figure of composite nanoparticle;
Figure 10 is Ag-SiO prepared by embodiment 9
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11
2the infrared spectrogram of composite nanoparticle;
Figure 11 is Ag-Ni-SiO prepared by embodiment 12
2the TEM electron microscopic picture of composite nanoparticle;
Wherein (a) represents resolution ratio is 50nm; B () represents resolution ratio is 20nm;
Figure 12 is Ag-Ni-SiO prepared by embodiment 12
2the grain size distribution of composite nanoparticle;
Figure 13 is Ag-Ni-SiO prepared by embodiment 12
2the EDS energy spectrogram of composite nanoparticle;
Figure 14 is Ag-Ni-SiO prepared by embodiment 13
2the TEM electron microscopic picture of composite nanoparticle;
Wherein (a) represents resolution ratio is 50nm; B () represents resolution ratio is 10nm;
Figure 15 is Ag-Ni-SiO prepared by embodiment 13
2the grain size distribution of composite nanoparticle;
Figure 16 is Ag-SiO prepared by embodiment 9
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11-13
2the uv-visible absorption spectroscopy figure of composite nanoparticle;
Figure 17 is Ag-SiO prepared by embodiment 9
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11-13
2the hysteresis curve of composite nanoparticle;
Figure 18 is Ag, Ag-SiO of the embodiment of the present invention 1 and embodiment 4-13
2with Ag-Ni-SiO
2the antibacterial qualitative experiment result figure of nano particle;
Wherein (a) represents original E. coli clones; B () represents embodiment 4; C () represents embodiment 5; D () represents embodiment 6; E () represents embodiment 7; F () represents embodiment 8; G () represents embodiment 9; H () represents embodiment 10; (i) represent embodiment 1; J () represents embodiment 11; K () represents embodiment 12; L () represents embodiment 13.
Detailed description of the invention
Embodiment of the present invention pulse laser used is YAG pulse laser.
Embodiment 1
A kind of Nano silver grain, its shape is spherical or elliposoidal, as shown in Figure 1, size range is 5 ~ 50nm, as shown in Figure 2, is mainly distributed in 15 ~ 35nm.
The laser controlling synthetic method of Nano silver grain is carried out according to following steps:
(1) target is prepared:
With granularity be micron-sized Ag powder for raw material, put into ball grinder and add ethanol and stir after 0.5h, in batch can, material adds steel ball and spring and carries out ball mill mixing 12h as abrasive material, and the weight ratio controlling drum's speed of rotation 300 turns/min, Ag powder and abrasive material is 6:1;
Ag powder through ball mill mixing is dried, then grinds 30min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 600 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 10Hz, laser energy density scope 50J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.2L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 30 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag nano particle.
Described liquid-phase collection system holds the collection container that promising volume fraction of ethanol is the deionized water of 10%, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 2
A kind of Nano silver grain, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of Nano silver grain is carried out according to following steps:
(1) target is prepared:
With granularity be micron-sized Ag powder for raw material, put into ball grinder and add ethanol and stir after 1h, in batch can, material adds steel ball and spring and carries out ball mill mixing 10h as abrasive material, and the weight ratio controlling drum's speed of rotation 400 turns/min, Ag powder and abrasive material is 6:1;
Ag powder through ball mill mixing is dried, then grinds 20min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 650 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 20Hz, laser energy density scope 80J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.5L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 20 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag nano particle.
Described liquid-phase collection system holds the collection container that promising volume fraction of ethanol is the deionized water of 30%, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 3
A kind of Nano silver grain, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of Nano silver grain is carried out according to following steps:
(1) target is prepared:
With granularity be micron-sized Ag powder for raw material, put into ball grinder and add ethanol and stir after 0.8h, in batch can, material adds steel ball and spring and carries out ball mill mixing 8h as abrasive material, and the weight ratio controlling drum's speed of rotation 350 turns/min, Ag powder and abrasive material is 6:1;
Ag powder through ball mill mixing is dried, then grinds 10min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 700 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 15Hz, laser energy density scope 60J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.4L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 10 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag nano particle.
Described liquid-phase collection system holds the collection container that promising volume fraction of ethanol is the deionized water of 50%, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 4
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 3wt.%SiO
2with 97wt.%Ag composition, its shape is spherical or elliposoidal, and as shown in Figure 3, size range is 5 ~ 50nm, and as shown in Figure 4, major part concentrates on 5 ~ 20nm.As can be seen from Figure 3, the dispersiveness of particle is better, this is because SiO
2add the reunion reducing nano silver particles.
The laser controlling synthetic method of silver composite nano particles is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 3wt.%SiO
2powder and 97wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, puts into ball grinder and adds ethanol and stir after 0.5h by composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 12h as abrasive material, and control drum's speed of rotation 300 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grinds 10min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 600 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 10Hz, laser energy density scope 50J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous and silica, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.2L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 28 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-SiO
2biphase compound particle.
Described liquid-phase collection system holds the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 5
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 5wt.%SiO
2with 95wt.%Ag composition, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of silver nanoparticle compound particle is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 5wt.%SiO
2powder and 95wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, puts into ball grinder and adds ethanol and stir after 1h by composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 11h as abrasive material, and control drum's speed of rotation 380 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grinds 20min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 620 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 20Hz, laser energy density scope 80J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous and silica, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.3L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 18 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-SiO
2biphase compound particle.
Described liquid-phase collection system holds the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 6
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 7wt.%SiO
2with 93wt.%Ag composition, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of silver nanoparticle compound particle is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 7wt.%SiO
2powder and 93wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, puts into ball grinder and adds ethanol and stir after 0.6h by composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 9h as abrasive material, and control drum's speed of rotation 320 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grinds 30min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 690 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 15Hz, laser energy density scope 65J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous and silica, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.4L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 30 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-SiO
2biphase compound particle.
Described liquid-phase collection system holds the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 7
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 9wt.%SiO
2with 91wt.%Ag composition, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of silver nanoparticle compound particle is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 9wt.%SiO
2powder and 91wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, puts into ball grinder and adds ethanol and stir after 0.8h by composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 8h as abrasive material, and control drum's speed of rotation 400 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grinds 15min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 680 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 12Hz, laser energy density scope 60J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous and silica, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.5L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 25 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-SiO
2biphase compound particle.
Described liquid-phase collection system holds the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 8
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 15wt.%SiO
2with 85wt.%Ag composition, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of silver nanoparticle compound particle is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 15wt.%SiO
2powder and 85wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, puts into ball grinder and adds ethanol and stir after 0.5h by composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 10h as abrasive material, and control drum's speed of rotation 350 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grinds 25min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 650 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 18Hz, laser energy density scope 70J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.2L/min, form gas phase forming core and the cluster of argentiferous and silica, being imported temperature is in the liquid-phase collection system of 20 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-SiO
2biphase compound particle.
Described liquid-phase collection system holds the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 9
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 20wt.%SiO
2with 80wt.%Ag composition, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
The laser controlling synthetic method of silver nanoparticle compound particle of the present invention is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 20wt.%SiO
2powder and 80wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, puts into ball grinder and adds ethanol and stir after 1h by composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 12h as abrasive material, and control drum's speed of rotation 300 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grinds 30min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 700 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 10Hz, laser energy density scope 50J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous and silica, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.3L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 15 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-SiO
2biphase compound particle.
Described liquid-phase collection system holds the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 10
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 30wt.%SiO
2with 70wt.%Ag composition, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
At the Ag-SiO that Fig. 5 Ag nano particle and heterogeneity form
2no matter in the uv-visible absorption spectra figure of composite nanoparticle, can see from its absorption curve, be Ag or Ag-SiO
2composite nanoparticle all has characteristic absorption peak near 400nm, and has a broadband to stretch to the path portion of ultraviolet wavelength region.When after interpolation silica, the ultraviolet-ray visible absorbing peak of nano silver particles there occurs blue shift in various degree, and by the silica compound with different content, changing the ultraviolet and visible absorption peak of Nano Silver, to realize optical property adjustable.
The laser controlling synthetic method of silver nanoparticle compound particle is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 30wt.%SiO
2powder and 70wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, puts into ball grinder and adds ethanol and stir after 0.5h by composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 8h as abrasive material, and control drum's speed of rotation 300 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grinds 25min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 600 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 20Hz, laser energy density scope 80J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.5L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 10 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-SiO
2biphase compound particle.
Described liquid-phase collection system holds the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 11
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 4wt.%Ni, 20wt.%SiO
2, surplus is Ag composition, and its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
Fig. 6 is Ag-Ni-SiO
2the TEM electron microscopic picture of composite nanoparticle, Fig. 7 is grain size distribution, and as can be seen from the figure, it is spherical that the shape of most of nano particle is, be elliposoidal on a small quantity, agglomeration does not appear in three-phase nano-complex particle, good dispersion.Can find out that from grain size distribution the domain size distribution of three-phase nano-complex particle is in the scope of 5nm ~ 35nm, narrow diameter distribution, and particle diameter accounts for more than 70% of total population in the population of 10nm ~ 20nm scope.Illustrate with the particle diameter of the standby three-phase nano-complex particle of gas evaporation-liquid-phase collection legal system smaller, this has great importance to bactericidal nano-silver.
Fig. 8 is the EDS energy spectrogram of the nano particle of 1 indication in Fig. 6 (a), the elemental composition showing compound particle in figure is Ag, Si, O and Ni, and the content of Ag is very high, and the content of nickel is very little, this is consistent with the composition of target, and nano-complex particle has mixed structure.
Fig. 9 is Ag-Ni-SiO
2the XRD figure of composite nanoparticle, can be drawn by XRD collection of illustrative plates, laser Gaseous evaporation-liquid-phase collection controls in the nano-complex particle of synthesis containing nickel, silver, silica, for the target product that will obtain, the generation of the impurity such as free from admixture silver oxide, nickel oxide, illustrates that the composite nanoparticle purity of preparation is high.
Figure 10 is Ag-SiO prepared by embodiment 9
2ag-Ni-SiO prepared by composite nanoparticle and the present embodiment
2the infrared spectrogram of composite nanoparticle, as can be seen from the figure, the compound of silica makes Si-O key strengthen further, and Si-O-Si antisymmetric stretching vibration peak is strengthened.Can draw thus, containing silica in the nano-complex particle of preparation, and be crystalline silica, without the introducing of other impurity, illustrates that the nano-complex particle purity of preparation is high.
The laser controlling synthetic method of silver composite nano particles is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 4wt.%Ni powder, 20wt.%SiO
2powder, surplus is Ag, is mixed into Ag-SiO
2-Ni three-phase composite powder, above-mentioned composite powder is put into ball grinder to add ethanol and stir after 0.5h, in batch can, expect that adding steel ball and spring carries out ball mill mixing 12h as abrasive material, control drum's speed of rotation 300 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Dry through the Ag powder of ball mill mixing or composite powder, then grind 30min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 600 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target or Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 15Hz, laser energy density scope 65J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.2L/min, form gas phase forming core and the cluster of argentiferous, nickel and silica, being imported temperature is in the liquid-phase collection system of 30 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-Ni-SiO
2three-phase composite nano particle.
Described liquid-phase collection system is the collection container of the deionized water holding promising volume fraction of ethanol 50%, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 12
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 7wt.%Ni, 20wt.%SiO
2, surplus is Ag composition, and its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
Figure 11 is Ag-Ni-SiO
2the TEM electron microscopic picture of composite nanoparticle, Figure 12 is grain size distribution, as can be seen from the figure, nano-complex particle is better dispersed, soilless sticking phenomenon produces, and nano-complex particle major part is the spherical of rule, and the particle size distribution range of nano-complex particle is narrow, in the scope of 10nm ~ 35nm, and the particle diameter of compound particle mainly concentrates in the scope of 15nm ~ 25nm.
Figure 13 is the energy spectrogram of indication composite nanoparticle 1 in Figure 11 (b), can see in nanocomposite particle and contain the elements such as O, Si, Ag, Ni, prove that compound particle is three-phase mixing composite construction from energy spectrogram.
The laser controlling synthetic method of silver composite nano particles is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 7wt.%Ni powder, 20wt.%SiO
2powder, surplus is Ag, is mixed into Ag-SiO
2-Ni three-phase composite powder, above-mentioned composite powder is put into ball grinder to add ethanol and stir after 1h, in batch can, expect that adding steel ball and spring carries out ball mill mixing 10h as abrasive material, control drum's speed of rotation 350 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Dry through the Ag powder of ball mill mixing or composite powder, then grind 20min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 650 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target or Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 20Hz, laser energy density scope 80J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.3L/min, form gas phase forming core and the cluster of argentiferous, nickel and silica, being imported temperature is in the liquid-phase collection system of 20 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-Ni-SiO
2three-phase composite nano particle.
Described liquid-phase collection system is the collection container of the deionized water holding promising volume fraction of ethanol 40%, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 13
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 10wt.%Ni, 20wt.%SiO
2, surplus is Ag composition, and its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
Figure 14 is Ag-Ni-SiO
2the TEM electron microscopic picture of composite nanoparticle, Figure 15 is grain size distribution, can find out in figure, the sharpness of border of nano-complex particle, good dispersion, nano particle soilless sticking phenomenon, the particle size distribution range of three-phase Nano Silver compound particle is wider, the particle diameter of small-particle is 6nm, and the particle diameter of macroparticle is 45nm, and particle diameter major part concentrates on 5 ~ 30nm.
Figure 16 is Ag-SiO prepared by embodiment 9
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11-13
2the uv-visible absorption spectroscopy figure of composite nanoparticle, as can be seen from ultravioletvisible absorption curve, compound particle has characteristic absorption peak and has a broadband to stretch to the path portion of ultraviolet wavelength region near 406nm, has silver to exist in the mixed sols that explanation gas evaporation-liquid-phase collection is formed.
Figure 17 is Ag-SiO prepared by embodiment 9
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11-13
2the hysteresis curve of composite nanoparticle, in figure, sample is containing 20%SiO
2, ni content is respectively 0%, and 4%, 7%, 10%.The saturation magnetization of a sample is 0.75996emu/g, and coercivity is 85.122G; B sample coercivity is 62.355G, and saturation magnetization is 1.5566emu/g; C sample coercivity is 92.656G, and saturation magnetization is 2.0740emu/g; D sample coercivity is 62.175G, and saturation magnetization is 2.4474emu/g.Along with the increase of Ni content, the saturation magnetization of three-phase nano-complex particle increases gradually, illustrate that there is certain humidification adding of Ni to the magnetic of nano-complex particle, after the novel nano compound particle magnetic enhancement of synthesis, be conducive to being reclaimed by magnetic selection method after application.
Ag, Ag-SiO of embodiment 1 and embodiment 4-13
2with Ag-Ni-SiO
2the antibacterial qualitative experiment result figure of nano particle as shown in figure 18, as can be seen from the figure, when culture medium only inoculates Escherichia coli, and when not adding Nano Silver and the compound particle colloidal sol of silver of laser controlling synthesis, a large amount of E. coli clones is had to grow on culture medium, as shown in figure (a).Its colony characteristics: color is milky, its shape mostly is circular, and colony edge is neat, smooth surface, surface and back side solid colour.Figure b ~ h is for the addition of SiO
2mass fraction is respectively 3%, and 5%, 7%, 9%, 15%, the Ag-SiO of 20%, 30%
2the flat board of two-phase composite nanoparticle, figure i is the flat board adding Ag nanoparticle sol, and to be the mass fraction that with the addition of Ni be figure g ~ l 4%, 7%, 10% and 20%SiO
2ag-Ni-SiO
2the flat board of three-phase composite nanoparticle sol.Can be clearly seen that from figure in b ~ l flat board and all do not have E. coli clones to grow, illustrate that the Nano Silver of synthesis and heterogeneous composite nanoparticle have obvious inhibitory action to colibacillary growth.
The laser controlling synthetic method of silver composite nano particles is carried out according to following steps:
(1) target is prepared:
According to percentage by weight, weighing granularity is micron-sized 10wt.%Ni powder, 20wt.%SiO
2powder, surplus is Ag, is mixed into Ag-SiO
2-Ni three-phase composite powder, above-mentioned composite powder is put into ball grinder to add ethanol and stir after 0.8h, in batch can, expect that adding steel ball and spring carries out ball mill mixing 8h as abrasive material, control drum's speed of rotation 400 turns/min, the weight ratio of composite powder and abrasive material is 6:1;
Dry through the Ag powder of ball mill mixing or composite powder, then grind 10min, add 504 adhesives and make cylindrical sample, dry 12h, then at N
2be heated to 700 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target or Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 10Hz, laser energy density scope 50J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, nickel and silica, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.5L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 10 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag-Ni-SiO
2three-phase composite nano particle.
Described liquid-phase collection system is contained with the collection container that volume fraction is 20% ethylene glycol+80% ethanol, is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
Embodiment 14
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 4wt.%Ni, 30wt.%SiO
2, surplus is Ag composition, and its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
Its laser controlling synthetic method is as different from Example 13 according to percentage by weight, and weighing granularity is micron-sized 4wt.%Ni powder, 30wt.%SiO
2powder, surplus is Ag, is mixed into Ag-SiO
2-Ni three-phase composite powder
Embodiment 15
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 6wt.%Ni, 3wt.%SiO
2, surplus is Ag composition, and its shape is spherical or elliposoidal, and size range is 5 ~ 50nm.
Its laser controlling synthetic method is as different from Example 13 according to percentage by weight, and weighing granularity is micron-sized 6wt.%Ni powder, 3wt.%SiO
2powder, surplus is Ag, is mixed into Ag-SiO
2-Ni three-phase composite powder.
Claims (5)
1. a laser controlling synthetic method for silver and silver composite nano particles, is characterized in that carrying out according to following steps:
(1) target is prepared:
With Ag powder for raw material, or according to percentage by weight, weigh 3 ~ 30wt.%SiO
2powder, 70 ~ 97wt.%Ag powder, be mixed into Ag-SiO
2two-phase composite powder, or weigh 4 ~ 10wt.%Ni powder, 3 ~ 30wt.%SiO
2powder, surplus is Ag powder, is mixed into Ag-SiO
2-Ni three-phase composite powder, puts into ball grinder and adds ethanol and stir after 0.5 ~ 1h by above-mentioned Ag powder or composite powder, in batch can, material adds steel ball and spring and carries out ball mill mixing 8 ~ 12h as abrasive material, controls drum's speed of rotation 300 ~ 400 turns/min;
Dry through the Ag powder of ball mill mixing or composite powder, then grind 10 ~ 30min, add binding agent and make cylindrical sample, dry 12h, then at N
2be heated to 600 ~ 700 DEG C under protection, insulation 1h, is cooled to 100 DEG C with stove, obtains Ag target or Ag composite target material, take out for subsequent use;
(2) laser ablation controls synthesis:
Above-mentioned target is placed in the rustless steel container of top tape quartz window, starts the pulse laser be positioned on workbench, the wavelength 1064nm of control impuls laser device laser bundle, frequency 10-20Hz, laser energy density scope 50-80J/mm
2, the X-Y-Z axle interlock of laser works platform, laser beam transparent quartz window carries out irradiation ablation to target, produces the plasma of argentiferous, passes into protection carrier gas N simultaneously
2, control flow rate of carrier gas 0.2-0.5L/min, form gas phase forming core and the cluster of argentiferous, being imported temperature is in the liquid-phase collection system of 10 ~ 30 DEG C, eventually passes Separation of Solid and Liquid and obtains Ag nano particle, Ag-SiO
2two-phase composite nanoparticle or Ag-Ni-SiO
2three-phase composite nano particle, its shape is spherical or elliposoidal, and size range is 5 ~ 50nm, Ag-Ni-SiO
2three-phase composite nano particle is three-phase mixing composite construction.
2. the laser controlling synthetic method of a kind of silver according to claim 1 and silver composite nano particles, is characterized in that described Ag powder, SiO
2powder and Ni powder are granularities is micron powder.
3. the laser controlling synthetic method of a kind of silver according to claim 1 and silver composite nano particles, is characterized in that the weight ratio of described Ag powder or composite powder and abrasive material is 6:1.
4. the laser controlling synthetic method of a kind of silver according to claim 1 and silver composite nano particles, is characterized in that described binding agent is 504 adhesives.
5. the laser controlling synthetic method of a kind of silver according to claim 1 and silver composite nano particles, it is characterized in that described liquid-phase collection system be hold promising volume fraction of ethanol be 10% ~ 50% deionized water or volume fraction be the collection container of 20% ethylene glycol+80% ethanol, liquid-phase system temperature controls, 10 ~ 30 DEG C of scopes, to be also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm in the middle part of described collection container.
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| CN104785251B (en) * | 2015-04-15 | 2017-10-13 | 中国科学院合肥物质科学研究院 | The synthetic method of many galactic nucleus/hollow mesoporous silicon oxide yolk shell structural nano reactor and its application |
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| CN106041060B (en) * | 2016-05-31 | 2018-02-16 | 华中科技大学 | A kind of method for preparing nano composite material using laser welding in the liquid phase |
| CN106077674B (en) * | 2016-06-16 | 2019-03-15 | 中国科学院合肥物质科学研究院 | A kind of silver nano-grain colloidal solution with efficient sterilizing performance |
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| US3787204A (en) * | 1970-07-24 | 1974-01-22 | Gkn Group Services Ltd | Production of composite materials containing coated inorganic fibers |
| CN1427041A (en) * | 2001-12-21 | 2003-07-02 | 中国科学院理化技术研究所 | Preparation method of spherical composite nano silver/silicon dioxide functional material |
| CN101111335A (en) * | 2005-02-02 | 2008-01-23 | 同和电子科技有限公司 | Silver particle powder and process for producing the same |
| CN103286312A (en) * | 2013-05-08 | 2013-09-11 | 复旦大学 | Surface-common-enhanced fluorescence surface-enhanced Raman multi-layer core-shell structure composite particles and preparation method of particles |
| CN103406548A (en) * | 2013-08-08 | 2013-11-27 | 广西大学 | Silver nano particle and preparation method and application thereof |
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| US3787204A (en) * | 1970-07-24 | 1974-01-22 | Gkn Group Services Ltd | Production of composite materials containing coated inorganic fibers |
| CN1427041A (en) * | 2001-12-21 | 2003-07-02 | 中国科学院理化技术研究所 | Preparation method of spherical composite nano silver/silicon dioxide functional material |
| CN101111335A (en) * | 2005-02-02 | 2008-01-23 | 同和电子科技有限公司 | Silver particle powder and process for producing the same |
| CN103286312A (en) * | 2013-05-08 | 2013-09-11 | 复旦大学 | Surface-common-enhanced fluorescence surface-enhanced Raman multi-layer core-shell structure composite particles and preparation method of particles |
| CN103406548A (en) * | 2013-08-08 | 2013-11-27 | 广西大学 | Silver nano particle and preparation method and application thereof |
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