CN103611928A - Ag and Ag-composite nanometer particles and laser control synthetic method thereof - Google Patents
Ag and Ag-composite nanometer particles and laser control synthetic method thereof Download PDFInfo
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Abstract
The invention belongs to the field of material technology, particularly relates to Ag and Ag-composite nanometer particles and a laser control synthetic method thereof. The Ag nanometer particle is in the sphere shape or the ellipsoid shape, and the size range of the Ag nanometer particle is 5-50 nm; the Ag nanometer-composite particle comprises, by weight, 3-30 % of SiO2 and 70-97 % of Ag, or 4-10 % of Ni and 3-30 % of SiO2, and the balance Ag. The synthetic method comprises the steps that first of all, target materials are prepared, then the wavelength of laser beams of a pulse laser is controlled to be 1064nm, the frequency of the laser beams is controlled to range from 10 Hz to 20 Hz, the range of the laser energy density is 50-80J/mm<2>, the laser beams carry out irradiation ablation on the target materials, the carrier gas N2 is introduced, gas phase nucleation and clusters including Ag and a composite phase are formed and guided into a liquid-phased collecting system with the temperature from 10 DEG C to 30 DEG C, and finally solid-liquid separation is conducted to obtain the Ag and Ag-compound nanometer particles. The Ag and Ag-compound nanometer particles can synthesize the nanometer particles with single-phased Ag, two-phased Ag-SiO2, three-phased Ag-Ni-SiO2 and larger-phased particles in an environment-friendly and disposable mode, and the synthesized nanometer particles have the advantages of being high in purity and good in dispersity, having the multi-phase mixed composite structure and the good antibacterial performance, and having the magnetic recycling function.
Description
Technical field
The invention belongs to material technology field, 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 materials that have been born.Wherein silver is that nano antibacterial agent becomes in recent years one of nano-functional material primary study and development both at home and abroad, that can tackle a pollution difficult problem.Natural disinfectant function due to silver (Ag), Nano silver grain can kill 650 various bacteria that comprise Escherichia coli in several minutes, the features such as having microbe killing properties can be strong, antibiotic property is lasting and nontoxic, the fields such as, air cleaning antibacterial at catalyst, sterilization, life science have broad application prospects.
Yet, 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 variation, and because silver-colored price is 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, be dispersed in the separation of the nano particle in processed liquid and removal process complexity and cost very high.Therefore, dispersiveness and the stability problem of solution nanoscale silver particle are that people study one of target of pursuit always.
Laser method is a kind of important method of synthesizing nano-particle because having the features such as synthesizing nano-particle purity is high, particle diameter is little, building-up process is simple, and wherein laser Gaseous ablation and liquid phase ablative method have important using value aspect synthetic silver and silver composite nano particles.Along with deepening continuously that people are familiar with Ag nano-complex particle, 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 good anti-microbial property, application cost is low and callable Novel silver nano-complex particle and laser new synthesis technology thereof, not only has important scientific research meaning but also has important using value.
These difficult problems of existence in applying around current Nano silver grain, people have mainly adopted the synthetic methods such as chemistry, physics and biology, carried out heterogeneous compound scientific research, and obtained many impressive progresses on nanoscale.By other metal (M), oxide (MO), polymer etc. to Nano silver grain carry out heterogeneous alloy, doping, load and composite modified after, formation Ag-M, Ag-MO, Ag-M-MO, Polymer-supported Ag etc. have the novel nano particle of 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, can obtain the character that single-particle does not have again, as optics adjustability (Ag-Cu, Ag-Ni, Ag@SiO
2), optical nonlinearity enhancement effect (Ag-Au, Cu
2o@Ag), the antibacterial (Ag-TiO of economic benefits and social benefits
2), magnetic gives (Ag-Ni, Ag-Fe
3o
4, NiAg@TiO
2) etc. character.Therefore, research and development Novel silver nano-complex particle and new synthetic method thereof, solve the many difficult problems that exist in the application of Ag nano particle significant.
Summary of the invention
For Nano silver grain in prior art, apply the problems such as the cost existing 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 is to control the key issues such as synthetic 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 pulse laser gas evaporation-liquid phase and collect and control synthetic silver nanoparticle compound particle.
A Nano silver grain, it is shaped as 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 forms, or by 4 ~ 10wt.% Ni, 3 ~ 30wt.% SiO
2, surplus is that Ag forms, and it is shaped as 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) prepare target:
Take Ag powder as 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 by above-mentioned Ag powder or composite powder and adds ethanol to stir after 0.5 ~ 1h, to material in batch can, adds steel ball and spring to carry out ball mill mixing 8 ~ 12h as abrasive material, controls turn/min of drum's speed of rotation 300 ~ 400;
Ag powder through ball mill mixing or composite powder are dried, then grind 10 ~ 30min, add binding agent to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 600 ~ 700 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target or Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 10 ~ 30 ℃, finally by mistake Separation of Solid and Liquid, obtain 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 that granularity 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 is that to hold promising volume fraction of ethanol be that 10% ~ 50% deionized water or volume fraction are the collection container of 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Compared with prior art, feature of the present invention and beneficial effect are:
The anti-microbial property of processing and utilizing Nano Silver of the present invention, also by utilizing heterogeneous nano combined heterogeneous synergistic mechanism, performance Ag, Ni, SiO
2each self-applying, through the one-tenth of science, be grouped into and be prepared into target, utilize the heterogeneous compound plasma of high energy laser ablation evaporation target to produce in gas phase simultaneously, reach while closing on nucleation concentration forming core under certain degree of supercooling, then at carrier gas N
2transporting under enter fast in liquid phase collection system coolingly fast, condense and be grown to nanometer or nano-complex particle; The appropriate surfactant ethylene glycol of liquid phase collection system clock carries out original position dispersion simultaneously, can improve the agglomeration of nano particle, the temperature of liquid phase collection system also can be carried out cooling control, in low temperature liquid phase, easily generate small size nano particle, the stainless (steel) wire of aperture 0.1 ~ 1mm is installed at liquid solution collection container, while making bubbles of carrier gas by fine-structure mesh, breaks and improve synthetic yield.In sum, in the growth course of liquid phase nanoparticles, by liquid-phase system being loaded to the impact of external force factor, thus the synthetic nano particle with different size, crystal formation, structure of controllability ground one-step method; Owing to containing high molecular surfactant in liquid-phase system, can carry out in-situ modification to nano-complex particle, form finely disseminated nano particle, reach and improved the object of reuniting.
The inventive method can environmental protection, disposable synthetic have single-phase, two-phase, three-phase and above novel nano compound particle thereof, and synthetic nano-complex particle 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 key dimension scope of synthetic nano-complex particle, at 5 ~ 50nm, is shaped as spherical or elliposoidal; Ag-SiO
2a little less than the magnetic of nano-complex particle, along with the increase of compound Ni content, 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 laser controlling synthetic method thereof that the present invention is synthetic have important application prospect.
Accompanying drawing explanation
Fig. 1 is the TEM Electronic Speculum picture of the Ag nano particle of the embodiment of the present invention 1 preparation;
Wherein (a) represents that resolution ratio is 50nm; (b) represent that resolution ratio is 20nm;
Fig. 2 is the particle diameter distribution map of the Ag nano particle of the embodiment of the present invention 1 preparation;
Fig. 3 is the standby Ag-SiO of embodiment of the present invention system 4
2the TEM Electronic Speculum picture of composite nanoparticle;
Wherein (a) represents that resolution ratio is 50nm; (b) represent that resolution ratio is 20nm;
Fig. 4 is that the embodiment of the present invention is prepared 4 Ag-SiO
2the particle diameter distribution map of composite nanoparticle;
Fig. 5 is the Ag nano particle of the embodiment of the present invention 1 preparation and Ag-SiO prepared by embodiment 4-10
2the uv-visible absorption spectra figure of composite nanoparticle;
Fig. 6 is the Ag-Ni-SiO of embodiment 11 preparations
2the TEM Electronic Speculum picture of composite nanoparticle;
Fig. 7 is the Ag-Ni-SiO of embodiment 11 preparations
2the particle diameter distribution map of composite nanoparticle;
Fig. 8 is the Ag-Ni-SiO of embodiment 11 preparations
2the EDS energy spectrogram of composite nanoparticle;
Fig. 9 is the Ag-Ni-SiO of embodiment 11 preparations
2the XRD figure of composite nanoparticle;
Figure 10 is the Ag-SiO of embodiment 9 preparations
2the Ag-Ni-SiO of composite nanoparticle and embodiment 11 preparations
2the infrared spectrogram of composite nanoparticle;
Figure 11 is the Ag-Ni-SiO of embodiment 12 preparations
2the TEM Electronic Speculum picture of composite nanoparticle;
Wherein (a) represents that resolution ratio is 50nm; (b) represent that resolution ratio is 20nm;
Figure 12 is the Ag-Ni-SiO of embodiment 12 preparations
2the particle diameter distribution map of composite nanoparticle;
Figure 13 is the Ag-Ni-SiO of embodiment 12 preparations
2the EDS energy spectrogram of composite nanoparticle;
Figure 14 is the Ag-Ni-SiO of embodiment 13 preparations
2the TEM Electronic Speculum picture of composite nanoparticle;
Wherein (a) represents that resolution ratio is 50nm; (b) represent that resolution ratio is 10nm;
Figure 15 is the Ag-Ni-SiO of embodiment 13 preparations
2the particle diameter distribution map of composite nanoparticle;
Figure 16 is the Ag-SiO of embodiment 9 preparations
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11-13
2the uv-visible absorption spectroscopy figure of composite nanoparticle;
Figure 17 is the Ag-SiO of embodiment 9 preparations
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11-13
2the hysteresis curve of composite nanoparticle;
Figure 18 is Ag, the 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 Escherichia coli bacterium colony; (b) represent embodiment 4; (c) represent embodiment 5; (d) represent embodiment 6; (e) represent embodiment 7; (f) represent embodiment 8; (g) represent embodiment 9; (h) represent embodiment 10; (i) represent embodiment 1; (j) represent embodiment 11; (k) represent embodiment 12; (l) represent embodiment 13.
The specific embodiment
Embodiment of the present invention pulse laser used is YAG pulse laser.
A Nano silver grain, it is shaped as 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) prepare target:
Take granularity as micron-sized Ag powder be raw material, put into ball grinder and add ethanol to stir after 0.5h, to material in batch can, add steel ball and spring to carry out ball mill mixing 12h as abrasive material, control turn/min of drum's speed of rotation 300, the weight ratio of Ag powder and abrasive material is 6:1;
Ag powder through ball mill mixing is dried, then grind 30min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 600 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 30 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag nano particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction of ethanol is 10% deionized water, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
A Nano silver grain, it is shaped as 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) prepare target:
Take granularity as micron-sized Ag powder be raw material, put into ball grinder and add ethanol to stir after 1h, to material in batch can, add steel ball and spring to carry out ball mill mixing 10h as abrasive material, control turn/min of drum's speed of rotation 400, the weight ratio of Ag powder and abrasive material is 6:1;
Ag powder through ball mill mixing is dried, then grind 20min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 650 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 20 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag nano particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction of ethanol is 30% deionized water, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
A Nano silver grain, it is shaped as 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) prepare target:
Take granularity as micron-sized Ag powder be raw material, put into ball grinder and add ethanol to stir after 0.8h, to material in batch can, add steel ball and spring to carry out ball mill mixing 8h as abrasive material, control turn/min of drum's speed of rotation 350, the weight ratio of Ag powder and abrasive material is 6:1;
Ag powder through ball mill mixing is dried, then grind 10min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 700 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 10 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag nano particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction of ethanol is 50% deionized water, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 3wt.% SiO
2form with 97wt.%Ag, it is shaped as 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, and this is because SiO
2add the reunion that has reduced nano silver particles.
The laser controlling synthetic method of silver composite nano particles is carried out according to following steps:
(1) prepare target:
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 by composite powder and adds ethanol to stir after 0.5h, in batch can, expects to add steel ball and spring to carry out ball mill mixing 12h as abrasive material, controls turn/min of drum's speed of rotation 300, and the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grind 10min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 600 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 28 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-SiO
2biphase compound particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 5wt.% SiO
2form with 95wt.%Ag, it is shaped as 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) prepare target:
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 by composite powder and adds ethanol to stir after 1h, in batch can, expects to add steel ball and spring to carry out ball mill mixing 11h as abrasive material, controls turn/min of drum's speed of rotation 380, and the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grind 20min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 620 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 18 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-SiO
2biphase compound particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Embodiment 6
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 7wt.% SiO
2form with 93wt.%Ag, it is shaped as 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) prepare target:
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 by composite powder and adds ethanol to stir after 0.6h, in batch can, expects to add steel ball and spring to carry out ball mill mixing 9h as abrasive material, controls turn/min of drum's speed of rotation 320, and the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grind 30min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 690 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 30 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-SiO
2biphase compound particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 9wt.% SiO
2form with 91wt.%Ag, it is shaped as 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) prepare target:
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 by composite powder and adds ethanol to stir after 0.8h, in batch can, expects to add steel ball and spring to carry out ball mill mixing 8h as abrasive material, controls turn/min of drum's speed of rotation 400, and the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grind 15min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 680 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 25 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-SiO
2biphase compound particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 15wt.% SiO
2form with 85wt.%Ag, it is shaped as 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) prepare target:
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 by composite powder and adds ethanol to stir after 0.5h, in batch can, expects to add steel ball and spring to carry out ball mill mixing 10h as abrasive material, controls turn/min of drum's speed of rotation 350, and the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grind 25min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 650 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 20 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-SiO
2biphase compound particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 20wt.% SiO
2form with 80wt.%Ag, it is shaped as 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) prepare target:
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 by composite powder and adds ethanol to stir after 1h, in batch can, expects to add steel ball and spring to carry out ball mill mixing 12h as abrasive material, controls turn/min of drum's speed of rotation 300, and the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grind 30min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 700 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 15 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-SiO
2biphase compound particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 30wt.% SiO
2form with 70wt.%Ag, it is shaped as spherical or elliposoidal, and size range is 5 ~ 50nm.
Ag-SiO at Fig. 5 Ag nano particle and heterogeneity composition
2no matter in the uv-visible absorption spectra figure of composite nanoparticle, from its absorption curve, can see, be Ag or Ag-SiO
2composite nanoparticle all has characteristic absorption peak near 400nm, and has a broadband to stretch to the track part in ultraviolet wavelength region.After adding silica, there is blue shift in various degree in the ultraviolet-ray visible absorbing peak of nano silver particles, and by compound with the silica of different content, it is adjustable that the ultraviolet and visible absorption peak of change Nano Silver realizes optical property.
The laser controlling synthetic method of silver nanoparticle compound particle is carried out according to following steps:
(1) prepare target:
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 by composite powder and adds ethanol to stir after 0.5h, in batch can, expects to add steel ball and spring to carry out ball mill mixing 8h as abrasive material, controls turn/min of drum's speed of rotation 300, and the weight ratio of composite powder and abrasive material is 6:1;
Composite powder through ball mill mixing is dried, then grind 25min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 600 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 10 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-SiO
2biphase compound particle.
Described liquid phase collection system is to hold the collection container that promising volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Embodiment 11
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 4wt.% Ni, 20wt.% SiO
2, surplus is that Ag forms, and it is shaped as spherical or elliposoidal, and size range is 5 ~ 50nm.
Fig. 6 is Ag-Ni-SiO
2the TEM Electronic Speculum picture of composite nanoparticle, Fig. 7 is particle diameter distribution map, as can be seen from the figure, most of nano particle be shaped as spherical, be elliposoidal on a small quantity, there is not agglomeration in three-phase nano-complex particle, good dispersion.The particle diameter that can find out three-phase nano-complex particle from particle diameter distribution map is distributed 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.The particle diameter that the three-phase nano-complex particle of preparing with gas evaporation-liquid phase collecting method is described is smaller, and 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 that has shown 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, by XRD collection of illustrative plates, can draw, laser Gaseous evaporation-liquid phase is collected to control in synthetic nano-complex particle and is contained 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 the Ag-SiO of embodiment 9 preparations
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 Si-O of the making key of silica is further strengthened, and Si-O-Si antisymmetric stretching vibration peak is strengthened.Can draw thus, in the nano-complex particle of preparation, contain silica, and be crystalline silica, without the introducing of other impurity, illustrate 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) prepare target:
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 adds ethanol to stir after 0.5h, in batch can, expect to add steel ball and spring to carry out ball mill mixing 12h as abrasive material, control turn/min of drum's speed of rotation 300, the weight ratio of composite powder and abrasive material is 6:1;
Ag powder through ball mill mixing or composite powder are dried, then grind 30min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 600 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target or Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 30 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-Ni-SiO
2three-phase composite nano particle.
Described liquid phase collection system is the collection container that holds the deionized water of promising volume fraction of ethanol 50%, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 7wt.% Ni, 20wt.% SiO
2, surplus is that Ag forms, and it is shaped as spherical or elliposoidal, and size range is 5 ~ 50nm.
Figure 11 is Ag-Ni-SiO
2the TEM Electronic Speculum picture of composite nanoparticle, Figure 12 is particle diameter distribution map, as can be seen from the figure, nano-complex particle is better dispersed, without agglomeration, produce, 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), from energy spectrogram, can find out in Nano composite granules and contain the elements such as O, Si, Ag, Ni, proves that compound particle is three-phase mixing composite construction.
The laser controlling synthetic method of silver composite nano particles is carried out according to following steps:
(1) prepare target:
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 adds ethanol to stir after 1h, in batch can, expect to add steel ball and spring to carry out ball mill mixing 10h as abrasive material, control turn/min of drum's speed of rotation 350, the weight ratio of composite powder and abrasive material is 6:1;
Ag powder through ball mill mixing or composite powder are dried, then grind 20min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 650 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target or Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 20 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-Ni-SiO
2three-phase composite nano particle.
Described liquid phase collection system is the collection container that holds the deionized water of promising volume fraction of ethanol 40%, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Embodiment 13
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 10wt.% Ni, 20wt.% SiO
2, surplus is that Ag forms, and it is shaped as spherical or elliposoidal, and size range is 5 ~ 50nm.
Figure 14 is Ag-Ni-SiO
2the TEM Electronic Speculum picture of composite nanoparticle, Figure 15 is particle diameter distribution map, in figure, can find out, the sharpness of border of nano-complex particle, good dispersion, nano particle is without agglomeration, 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 the Ag-SiO of embodiment 9 preparations
2ag-Ni-SiO prepared by composite nanoparticle and embodiment 11-13
2the uv-visible absorption spectroscopy figure of composite nanoparticle, from UV, visible light absorption curve, can find out, compound particle has characteristic absorption peak and has a broadband to stretch to the track part in ultraviolet wavelength region near 406nm, illustrates by gas evaporation-liquid phase and collects in the mixed sols forming and have silver to exist.
Figure 17 is the Ag-SiO of embodiment 9 preparations
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%, 4%, and 7%, 10%.The saturation magnetization of a sample is 0.75996 emu/g, and coercivity is 85.122 G; B sample coercivity is 62.355 G, and saturation magnetization is 1.5566 emu/g; C sample coercivity is 92.656 G, and saturation magnetization is 2.0740 emu/g; D sample coercivity is 62.175 G, and saturation magnetization is 2.4474emu/g.Increase along with Ni content, the saturation magnetization of three-phase nano-complex particle increases gradually, illustrate and adding of Ni the magnetic of nano-complex particle is had to certain humidification, after synthetic novel nano compound particle magnetic enhancement, be conducive to by magnetic selection method, reclaim after application.
The Ag of embodiment 1 and embodiment 4-13, Ag-SiO
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, on culture medium, only inoculate Escherichia coli, and do not add the synthetic Nano Silver of laser controlling and silver compound particle colloidal sol time, there is a large amount of Escherichia coli bacterium colonies to grow on culture medium, as shown in figure (a).Its colony characteristics: color is milky, it is circular that its shape mostly is, and colony edge is neat, smooth surface, surface and back side solid colour.Figure b～h is for having added SiO
2mass fraction is respectively 3%, 5%, and 7%, 9%, 15%, 20%, 30% Ag-SiO
2the flat board of two-phase composite nanoparticle, figure i is the flat board that has added Ag nanoparticle sol, figure g～l is that the mass fraction that added Ni is 4%, 7%, 10% and 20%SiO
2ag-Ni-SiO
2the flat board of three-phase composite nanoparticle sol.From figure, can be clearly seen that in b～l flat board and all there is no Escherichia coli colony growth, illustrate that synthetic Nano Silver 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) prepare target:
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 adds ethanol to stir after 0.8h, in batch can, expect to add steel ball and spring to carry out ball mill mixing 8h as abrasive material, control turn/min of drum's speed of rotation 400, the weight ratio of composite powder and abrasive material is 6:1;
Ag powder through ball mill mixing or composite powder are dried, then grind 10min, add 504 adhesives to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 700 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target or Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 10 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag-Ni-SiO
2three-phase composite nano particle.
Described liquid phase collection system is to be contained with the collection container that volume fraction is 20% ethylene glycol+80% ethanol, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
Embodiment 14
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 4wt.% Ni, 30wt.% SiO
2, surplus is that Ag forms, and it is shaped as 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
Silver nanoparticle compound particle, its chemical composition by weight percentage, by 6wt.% Ni, 3wt.% SiO
2, surplus is that Ag forms, and it is shaped as 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 (7)
1. a Nano silver grain, is characterized in that it is shaped as spherical or elliposoidal, and size range is 5 ~ 50nm.
2. a silver composite nano particles, is characterized in that chemical composition by weight percentage, by 3 ~ 30wt.% SiO
2, 70 ~ 97wt.%Ag forms, or by 4 ~ 10wt.% Ni, 3 ~ 30wt.% SiO
2, surplus is that Ag forms, and it is shaped as spherical or elliposoidal, and size range is 5 ~ 50nm.
3. as the laser controlling synthetic method of claim 1 or a kind of silver claimed in claim 2 and silver composite nano particles, it is characterized in that carrying out according to following steps:
(1) prepare target:
Take Ag powder as 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 by above-mentioned Ag powder or composite powder and adds ethanol to stir after 0.5 ~ 1h, to material in batch can, adds steel ball and spring to carry out ball mill mixing 8 ~ 12h as abrasive material, controls turn/min of drum's speed of rotation 300 ~ 400;
Ag powder through ball mill mixing or composite powder are dried, then grind 10 ~ 30min, add binding agent to make cylindrical sample, dry 12h, then at N
2under protection, be heated to 600 ~ 700 ℃, insulation 1h, is cooled to 100 ℃ with stove, obtains Ag target or Ag composite target material, takes out standby;
(2) laser ablation is controlled synthetic:
Above-mentioned target is placed in to the rustless steel container of top band quartz window, starts and be positioned at the pulse laser 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 sees through quartz window target is carried out to irradiation ablation, 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, is imported temperature and be in the liquid phase collection system of 10 ~ 30 ℃, finally by mistake Separation of Solid and Liquid, obtain Ag nano particle, Ag-SiO
2two-phase composite nanoparticle or Ag-Ni-SiO
2three-phase composite nano particle.
4. the laser controlling synthetic method of a kind of silver according to claim 3 and silver composite nano particles, is characterized in that described Ag powder, SiO
2powder and Ni powder are that granularity is micron powder.
5. the laser controlling synthetic method of a kind of silver according to claim 3 and silver composite nano particles, is characterized in that described Ag powder or the weight ratio of composite powder and abrasive material are 6:1.
6. the laser controlling synthetic method of a kind of silver according to claim 3 and silver composite nano particles, is characterized in that described binding agent is 504 adhesives.
7. the laser controlling synthetic method of a kind of silver according to claim 3 and silver composite nano particles, it is characterized in that described liquid phase collection system is that to hold promising volume fraction of ethanol be that 10% ~ 50% deionized water or volume fraction are the collection container of 20% ethylene glycol+80% ethanol, liquid-phase system temperature is controlled at 10 ~ 30 ℃ of scopes, and described collection container middle part is also provided with the stainless (steel) wire of three layers of aperture 0.1 ~ 1mm.
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| CN104785251A (en) * | 2015-04-15 | 2015-07-22 | 中国科学院合肥物质科学研究院 | Synthesis method and application of nanoreactor with multi-silver core/hollow mesoporous silica yolk shell structure |
| CN105076206A (en) * | 2014-05-09 | 2015-11-25 | 中国人民解放军63971部队 | Magnetic porous nano silver antibacterial material, preparation method and application |
| CN105689727A (en) * | 2016-01-29 | 2016-06-22 | 中国工程物理研究院流体物理研究所 | Method for preparing solid-dissolved high-bactericidal-activity nanometer Ag-Cu alloy powder by means of in-liquid pulse energy technology |
| CN106041060A (en) * | 2016-05-31 | 2016-10-26 | 华中科技大学 | Method for preparing nanocomposite through laser welding in liquid phase |
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| GB1373485A (en) * | 1970-07-24 | 1974-11-13 | Gkn Group Services Ltd | Production of compotie materials |
| CN1198884C (en) * | 2001-12-21 | 2005-04-27 | 中国科学院理化技术研究所 | Preparation method of spherical composite nano silver/silicon dioxide functional material |
| JP4284283B2 (en) * | 2005-02-02 | 2009-06-24 | Ｄｏｗａエレクトロニクス株式会社 | Silver particle powder manufacturing method |
| 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 |
| CN103406548B (en) * | 2013-08-08 | 2015-11-18 | 广西大学 | Nano silver grain and preparation method thereof and application |
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| CN105689727A (en) * | 2016-01-29 | 2016-06-22 | 中国工程物理研究院流体物理研究所 | Method for preparing solid-dissolved high-bactericidal-activity nanometer Ag-Cu alloy powder by means of in-liquid pulse energy technology |
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| CN106077674A (en) * | 2016-06-16 | 2016-11-09 | 中国科学院合肥物质科学研究院 | A kind of silver nano-grain colloid solution with efficient sterilizing performance |
| CN107728469A (en) * | 2017-08-28 | 2018-02-23 | 三维泰柯（厦门）电子科技有限公司 | A kind of laser particle control method |
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