CN103111246A - Preparation method of nanoparticle size standard substance - Google Patents
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Abstract
The invention relates to the field of nano-size powder, and in particular relates to a preparation method of nanoparticle size standard substances. The nanoparticle size standard substance is prepared by the following steps of: preparing microspheres from lauryl sodium sulfate which is taken as an emulsifying agent and potassium persulfate which is taken as a triggering agent through a soap-free emulsion polymerization method; and further screening and separating the microspheres through a field-flow fractionation technology to obtain the nanoparticle size standard substances. The prepared microspheres have the advantages of high uniformity, high degree of sphericity, high stability and the like. Major achievements disclosed by the invention are at an international advanced level, and play an important role in future effective size traceability of nanoparticle sizes.
Description
Technical field
The present invention relates to nanoscale powder field, relate in particular to a kind of preparation method of nano particle scale calibration material.
Technical background
Along with the development of powder technology and nanosecond science and technology, day by day urgent to the detection demand of sub-micron and nanoscale powder, the nanometer detection means also are more and more diversified, and this just requires to adapt to the calibration substance that the Nano grade detecting instrument uses.The nanometer particle size standard substance is to have the microballoon that definite particle size values and extremely narrow particle diameter distribute, when it can be used for measure bacterium, virus, ribosomes and cellule material size as the reference material of proofreading and correct, can be to the correction of granulometry means, to research field, the chromatography of dynamic light scattering and colloidal dispersion, organize separation technology field to be significant.The standard substance (the SRM-U.S. is to the abbreviation of standard substance) that USA National Institute of Standard and Technology (National Institute for Standards and Technology-NIST) provides is considered to have authority in the world, 8 kinds of polystyrene microsphere country's secondary reference materials for particle size analysis and 2 kinds of one-level reference materials for particle size analysis, size range is between the 2-75 micron, and is but expensive.
Emulsion polymerisation (Emulsion Polymerazition) is an important method in the macromolecule prior synthesizing method, is in polymerisation in bulk, grows up in the improvement of the methods such as polymerisation in solution and suspension polymerisation.It is in early days for the preparation of one of important method of high polymer micro balloons, can synthesize the microballoon that particle diameter is 10-500nm.Emulsion polymerisation is comprised of continuous phase medium (being generally water), oil-soluble monomer, emulsifying agent, water soluble starter etc.But emulsion system need to add a large amount of emulsifying agents to be stablized.Therefore, can a large amount of emulsifying agent molecules residually be arranged on the surface of product, affect the surface property of material, the performances such as electrical property, resistance to water.And it is very difficult to remove these emulsifying agents, has greatly increased production cost.Simultaneously, the conversion ratio of emulsion polymerisation is very low.
Emulsifier-free emulsion polymerization (Soap-free Emulsion Polymerization) is emerging in recent years a kind of polymerization, and it is to improve and get on the basis of conventional emulsion polymerization.Traditional emulsion polymerisation need to add a large amount of emulsifying agents, is adsorbed on the surface of monomer droplet and increase-volume micella, although can make the stable while of emulsion system also bring many problems.Particularly the emulsifying agent molecule still can be adsorbed on the surface of product, affects the mechanical property of product, optical property, electrical property, the performances such as surface property and resistance to water.Emulsifier-free emulsion polymerization is a kind of new polymerization that grows up on the basis of emulsion polymerisation, a kind of emulsion polymerisation that refers to not add emulsifying agent in system or only add a small amount of emulsifying agent (concentration is lower than CMC).The characteristics of emulsifier-free emulsion polymerization: 1) made microsphere surface relatively " cleaning ", avoided many drawbacks that emulsifying agent brings in the conventional emulsion polymerization, large such as emulsifying agent consumption, thus can not from polymer, remove the purity that affects product and performance etc. fully.2) microballoon of hydrophily functional group can be preparation table worn, also hud typed hydrophobicity, Hydrophilic polymeric microspheres can be prepared; 3) the latex particle monodispersity of gained is good, and particle diameter is also large than conventional emulsion polymerization, can be near micron order.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method who adopts the standby microballoon of emulsifier-free emulsion polymerization legal system, field flow isolation technics further to screen the nano particle scale calibration material of separation, prepared microballoon has uniformity, good sphericity, stable advantages of higher.
The present invention realizes by following technology:
A kind of preparation method of nano particle scale calibration material is characterized in that adopting the emulsifier-free emulsion polymerization legal system standby, and it specifically may further comprise the steps:
Step 1: polystyrene synthetic
1) cinnamic purifying: styrene is placed separatory funnel, the concentration that adds 0.5～3 times of volume is the washing 2～4 times of fully vibrating of 5% sodium hydroxide solution, keep the upper strata styrene solution, to remove the polymerization inhibitor in the styrene, with distilled water styrene is washed till neutrality again, the NaOH that flush away is residual, then the styrene after will washing places round-bottomed flask to add calcium oxide and removes residual water, styrene is placed dry round-bottomed flask, decompression distillation under the protection of nitrogen, collect the cut under the 0.08MPa, then cut low temperature under the protection of nitrogen of collecting is preserved;
2) synthetic: the 3～6mmol/L lauryl sodium sulfate aqueous solution that in churned mechanically four-hole round-bottomed flask, adds 90～150ml, stir 10～30min, pass into simultaneously the nitrogen deoxygenation, then with reaction unit as in 80～90 ℃ of water-baths, adding 3～5ml is dissolved with the above-mentioned styrene of 0.03～0.15g initator, react and to obtain nattier blue granules of polystyrene emulsion in 4～5 hours, remain nitrogen protection in the course of reaction;
3) separation of product and purification: adding divalence or Tricationic salt demulsifier carry out breakdown of emulsion in the granules of polystyrene emulsion of gained, granules of polystyrene is assembled, emulsion is by the original blue translucent white depositions suspension that become, with discarding supernatant liquor after this suspension centrifugation, can obtain the nano particle of polystyrene; The product of gained is added absolute ethyl alcohol, fully vibration makes its dispersion on the sonic oscillation cleaning machine, and then centrifugation, discards supernatant liquor, so repeatedly clean 2～4 times, the product after cleaning was namely obtained the product of white powder 60 ℃ of oven dry in 12 hours;
Step 2: the screening of nano pipe/polyhenylethylene mono-dispersion microballoon with separate
Adopt the AF2000 MT – Field-Flow Fractionation type field flow separator of German Postnova analytics company, carry out single or the repeated multiple times directly separation of polystyrene microsphere of simple grain, make the following nano particle scale calibration material of 100nm particle diameter; In 80-150ml water or ethanolic solution, be 1ml/min at Tip flow with the 1g sample dissolution, Focus flow is 1ml/min, and Cross flow is each sample introduction 1ml under the condition of 1ml/min; Collect respectively the component of different time sections, and get final product.
Described emulsifying agent is lauryl sodium sulfate, dodecyl sodium sulfate or neopelex; Described initator is potassium peroxydisulfate, azo-bis-isobutyrate hydrochloride or azo two isobutyl imidazoline salt hydrochlorates; Described demulsifier is alchlor or changes magnesium or calcium chloride.
Soap-free polymerization method mechanism of the present invention: owing to do not contain or only contain emulsifying agent in the emulsifier-free emulsion polymerization system, the mechanism of nucleation of traditional emulsion polymerisation can't be explained.People just begin the mechanism of nucleation of emulsifier-free emulsion polymerization is conducted in-depth research since last century, at present by generally accepted homogeneous nucleation and the two kinds of theories of Oligomeric micellar nucleation of mainly containing of people.The human gel chromatographies such as Oligomeric micellar mechanism of nucleation: Goodwall are studied cinnamic emulsifier-free emulsion polymerization with the projection Electronic Speculum, have proposed the Oligomeric micellar mechanism of nucleation.This mechanism is thought, at the initial stage of polymerisation, at first generates a large amount of oligomers at aqueous phase, and an end is with hydrophilic initator fragment, and the other end is polymer chain.Here it is they have been had must surface-active action, when these oligomers had reached critical micelle concentration, will flock together formed the oligomerisation micella, simultaneously increase-volume monomer.This has just formed the emulsion particle in the conventional emulsion polymerization.Present stage, the mechanism of polymerization of emulsifier-free emulsion polymerization mainly was the Oligomeric micellar mechanism of nucleation that is proposed by Goodall.In the system of beginning, aqueous phase generates a large amount of oligomers, and these oligomer one ends are the hydrophilic group of initator, and the other end is polymer chain.Like this, after oligomer rises to certain-length just and a small amount of emulsifying agent and other oligomers of aqueous phase form Oligomeric micellar, simultaneously all right increase-volume monomer.So far just formed the emulsion particle in the classical emulsion polymerisation.
It is that a kind of new compartment analysis is theoretical that field flow separates (Field Flow Fractionation, FFF).It cooperates with sample with fluid and impressed field, thereby realizes the separation of component in the sample.As a class isolation technics, that field flow separates is separable, purify and collect that particle size range is the suspended particle of 20 nm ~ 1 μ m in the fluid.The present invention has adopted the AF2000 MT – Field-Flow Fractionation type field flow separator of German Postnova analytics company.Its principle that adopts is to apply a field of flow that consists of with same solvent in the vertical direction of fluid flow direction to it, relies on particle to flow in solvent and realizes separating with the difference of diffusion coefficient.The fluid field field of force flow point that adopts has added a focusing system in method.Be the focus flow among Figure 10.Separation theorem is added the field flow power perpendicular to its flow direction and is come the nano particle in the sample fluid is separated as mentioned above in horizontal sample fluid.
The present invention compared with prior art has the following advantages: the present invention is take lauryl sodium sulfate as emulsifying agent, potassium peroxydisulfate is initator, the standby microballoon of emulsifier-free emulsion polymerization legal system, adopt the field flow isolation technics further to screen the nano particle scale calibration material of separation, prepared microballoon has uniformity, good sphericity, stable advantages of higher.Main achievement of the present invention is in international most advanced level, to effectively the yardstick of nano particle diameter being traced to the source and will be played an important role from now on.
Description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Accompanying drawing 1 is that the granules of polystyrene of the embodiment of the invention 1 separates spectrogram;
Accompanying drawing 2 is polystyrene microsphere separation condition figure of the embodiment of the invention 1;
Accompanying drawing 3 is the SEM figure before and after the polystyrene mono-dispersion microballoon of the embodiment of the invention 1 separates;
Accompanying drawing 4 is scatter charts of the polystyrene microsphere particle diameter of the embodiment of the invention 1;
Accompanying drawing 5 is study on the stability SEM figure comparison diagrams of the polystyrene microsphere of the embodiment of the invention 1;
Accompanying drawing 6 is that the granules of polystyrene of the embodiment of the invention 2 separates spectrogram;
Accompanying drawing 7 is granules of polystyrene separation condition figure of the embodiment of the invention 2;
Accompanying drawing 8 is the SEM figure comparison diagrams before and after the granules of polystyrene microballoon of the embodiment of the invention 2 separates;
Accompanying drawing 9 is scatter charts of the polystyrene microsphere particle diameter of the embodiment of the invention 2;
Accompanying drawing 10 is AF2000 MT – Field-Flow Fractionation type field flow separator principle schematic of the present invention.
The specific embodiment
The invention will be further described below by embodiment, and accompanying drawing is specific embodiments of the invention.
Embodiment 1:The preparation of particle diameter 90nm polystyrene microsphere
1, polystyrene is synthetic
1) cinnamic purifying: 50mL styrene is placed the 150mL pear shape separatory funnel, discard lower floor's sodium hydroxide solution after 5% the sodium hydroxide solution that adds that 50mL configured fully vibrates, then according to above-mentioned steps styrene solution is cleaned three times.The purpose of this step is in order to remove the polymerization inhibitor in the styrene.With distilled water styrene is washed till neutrality again, purpose is for the residual NaOH of flush away.Then the styrene after will washing places round-bottomed flask to add an amount of calcium oxide and removes residual water.The styrene of flush away polymerization inhibitor is placed dry round-bottomed flask, and the cut under the 0.08MPa is collected in decompression distillation under the protection of nitrogen.Then cut low temperature under the protection of nitrogen of collecting is preserved.
2) synthetic: as in churned mechanically 250ml four-hole round-bottomed flask, to add 120ml water and 0.1039g lauryl sodium sulfate.Stir 10-30min with the abundant dissolving of assurance emulsifying agent and stablizing of emulsion particle.Pass into simultaneously the nitrogen deoxygenation, the deoxygenation time is about half an hour.Then with reaction unit as in 80 ℃ of water-baths, add the above-mentioned styrene of 3ml be dissolved with the 0.03g potassium peroxydisulfate, can obtain the emulsions of polymer in 5 hours 80 ℃ of lower reactions.Remain nitrogen protection (flow velocity be about 2 ~ 5 bubbles/minute) in the course of reaction.
3) separation of product and purification: add the alchlor breakdown of emulsion of 2g at the emulsion product of gained, granules of polystyrene has produced obvious clustering phenomena.Emulsion has become white depositions suspension by original blue translucent solution.With discarding the upper strata stillness of night after this suspension centrifugation, can obtain the nano particle of polystyrene.In order to remove initator residual in the product, emulsifying agent and styrene monomer add absolute ethyl alcohol with the product of gained, and fully vibration makes its dispersion on the sonic oscillation cleaning machine, and then centrifugation, discards supernatant liquor.So repeatedly clean three times, residual impurity is removed, the product after cleaning was namely obtained the product of white powder 60 ℃ of oven dry in 12 hours.
2, the screening of nano pipe/polyhenylethylene mono-dispersion microballoon with separate (particle diameter 90nm)
Adopt the AF2000 MT – Field-Flow Fractionation type field flow separator of German Postnova analytics company, carry out the separation of single or repeated multiple times simple grain footpath polystyrene microsphere, make the polystyrene microsphere of particle diameter 90nm.In the water or ethanolic solution of 100ml, be 1ml/min at Tip flow with the 1g sample dissolution, Focus flow is 1ml/min, and Cross flow is each sample introduction 1ml under the condition of 1ml/min; Carry out sample collection take 14-16 minute as collector unit, namely get particle diameter 90nm polystyrene microsphere.
Accompanying drawing 1 is the separation graph of the Nano grade mono-dispersion microballoon about 90nm, and abscissa is the time, and ordinate is the signal strength signal intensity (being directly proportional with the concentration of microballoon) of detector.By principle as can be known, the peak is the detached peaks of microballoon among the figure.Beginning in 12 minutes, detector just begin to detect microballoon appearance.As time goes on, the microballoon of separation has arrived the highest concentration.The concentration of microballoon just fades away after 17 minutes.By this kind method, under the early stage synthetic prerequisite of size ratio than homogeneous, with sample separation, carry out sample collection take 14-16 minute as collector unit by the field flow isolation technics.
Accompanying drawing 3 is the SEM figure before and after the polystyrene mono-dispersion microballoon about 90nm separates.Figure a is the SEM figure before separating, and figure b is the SEM figure after separating.Can find out in the particle diameter distribution and be improved to some extent.PS particle after the separation is measured through Shandong Forecasting and Analysis Center, and particle diameter is 90nm.
3, the inhomogeneity investigation of PS microballoon
As the standard substance that particle diameter is measured, the definite value of particle diameter and the uniformity of particle diameter are important aspects.We come particle diameter and particle diameter distribution are carried out statistics quantitative by a large amount of samples being carried out the particle diameter definite value.Experimental result is seen Fig. 4: come the sample particle diameter is carried out statistical measurement by measuring a large amount of sample particles.Fig. 4 is the scatter chart of particle diameter.As can be seen from the figure, the particle diameter more than 90% all is distributed within the 88nm-92nm scope.Result in this and the test report is very close.The uniformity of particle diameter is also very high simultaneously.
4, the investigation of PS polymeric microspheres stabilize
Nano step standard matter is the benchmark as Nano grade length, simultaneously in actual use consumption seldom, the operating period limit for length of single batch of sample.Therefore, stability also is an important parameter of standard substance preferably.Stability to microballoon is also investigated.Mainly investigated in water and two kinds of dissimilar solvents of ethanol, whether microballoon has Swelling.And the holding time of suitable prolongation in volume investigate the stability of microballoon.Investigate the stability of sample at the SEM of different times figure by following the tracks of one batch of sample.
Fig. 5 is that particle diameter is the SEM picture of the polystyrene microsphere of 90nm.Left figure was taken in November, 2011, and right figure was taken in May, 2012.Can find out that uniformity and the sphericity of microballoon do not have significant change, sample has preferably stability.
Embodiment 2:The preparation of particle diameter 50nm polystyrene microsphere
1, polystyrene is synthetic
1) cinnamic purifying: 50mL styrene is placed the 150mL pear shape separatory funnel, discard lower floor's sodium hydroxide solution after 5% the sodium hydroxide solution that adds that 50mL configured fully vibrates, then according to above-mentioned steps styrene solution is cleaned three times.The purpose of this step is in order to remove the polymerization inhibitor in the styrene.With distilled water styrene is washed till neutrality again, purpose is for the residual NaOH of flush away.Then the styrene after will washing places round-bottomed flask to add an amount of calcium oxide and removes residual water.The styrene of flush away polymerization inhibitor is placed dry round-bottomed flask, and the cut under the 0.08MPa is collected in decompression distillation under the protection of nitrogen.Then cut low temperature under the protection of nitrogen of collecting is preserved.
2) synthetic: as in churned mechanically 250ml four-hole round-bottomed flask, to add 120ml water and 0.1558g lauryl sodium sulfate.Stir 10-30min with the abundant dissolving of assurance emulsifying agent and stablizing of emulsion particle.Pass into simultaneously the nitrogen deoxygenation, the deoxygenation time is about half an hour.Then with reaction unit as in 80 ℃ of water-baths, add the above-mentioned styrene of 3ml be dissolved with the 0.03g potassium peroxydisulfate.Can obtain the emulsion of polymer in 5 hours 80 ℃ of lower reactions.Remain nitrogen protection (flow velocity be about 2 ~ 5 bubbles/minute) in the course of reaction.
3) separation of product and purification: add the alchlor breakdown of emulsion of 2g at the emulsion product of gained, granules of polystyrene has produced obvious clustering phenomena.Emulsion has become white depositions suspension by original blue translucent solution.With discarding the upper strata stillness of night after this suspension centrifugation, can obtain the nano particle of polystyrene.In order to remove initator residual in the product, emulsifying agent and styrene monomer add absolute ethyl alcohol with the product of gained, and fully vibration makes its dispersion on the sonic oscillation cleaning machine, and then centrifugation, discards supernatant liquor.So repeatedly clean three times, residual impurity is removed, the product after cleaning was namely obtained the product of white powder 60 ℃ of oven dry in 12 hours.
2, the screening of nano pipe/polyhenylethylene mono-dispersion microballoon with separate (particle diameter 50nm)
Adopt the AF2000 MT – Field-Flow Fractionation type field flow separator of German Postnova analytics company, carry out the separation of single or repeated multiple times simple grain footpath polystyrene microsphere, the polystyrene microsphere of preparation particle diameter 50nm.In the water or ethanolic solution of 80～150ml, be 1ml/min at Tip flow with the 1g sample dissolution, Focus flow is 1ml/min, and Cross flow is each sample introduction 1ml under the condition of 1ml/min; Collect 12-14 minute component, namely get particle diameter 50nm polystyrene microsphere.
Accompanying drawing 6 is that particle diameter is the separation spectrogram of the polystyrene microsphere about 50nm, and abscissa is the time among the figure, and ordinate is the signal strength signal intensity (being directly proportional with the concentration of microballoon) of detector.By above-mentioned principle as can be known, red peak is the detached peaks of microballoon in the way.Beginning in 10 minutes, detector just begin to detect microballoon appearance.As time goes on, the microballoon of separation has arrived the highest concentration.The concentration of microballoon just fades away after 15 minutes.By this kind method, under the early stage synthetic prerequisite of size ratio than homogeneous, with sample separation, carry out sample collection take 12-14 minute as collector unit by the field flow isolation technics.
Accompanying drawing 7 is that particle diameter is the separation condition figure of the polystyrene microsphere about 50nm.Abscissa is the time, and ordinate is flow velocity, and Tip Flow is sample fluid, Cross Flow is that field flow body, Focus Flow are for focusing on fluid.In conjunction with separating spectrogram as can be known, front 5 minutes is the sample injection time of system, and during this period of time Tip Flow and Focus Flow convection current can be concentrated and separate sample in certain separated region.Since the 5th minute, along with the minimizing of Focus Flow and the increase of Tip Flow, sample has flowed to detector end gradually, because the centrifugation in early stage, this stage Cross Flow reduction gradually is so that the particle that bulky grain is crushed on the collecting layer is able to flow to detector with sample fluid.
Fig. 8 is the SEM figure contrast of the separation front and back of 50nm left and right sides microballoon.Figure a is the polystyrene microsphere SEM figure before separating.Figure b is the SEM figure after separating.We can find out from figure, the rough surface of particle before separation, and particle size uniformity is relatively poor.The general effect of SEM is not fine.SEM after contrast separates can find out that the smoothness of the particle surface after the separation has had raising to a certain degree.Raising has to a certain degree also been arranged on particle size uniformity.Of course, the field flow isolation technics can well be applied in the separating experiment of Nano grade particle.Effect with good separation.
PS particle after the separation is measured through Shandong Forecasting and Analysis Center, and particle diameter is 52nm.
3, the inhomogeneity investigation of PS microballoon
As the standard substance that particle diameter is measured, the definite value of particle diameter and the uniformity of particle diameter are important aspects.We come particle diameter and particle diameter distribution are carried out statistics quantitative by a large amount of samples being carried out the particle diameter definite value.Experimental result sees that accompanying drawing 9: Fig. 9 is that particle diameter is the scatter chart of the polystyrene microsphere of 50nm.As can be seen from the figure, the particle diameter more than 90% all is distributed within the 50nm-54nm scope.Result in this and the test report is very close.The uniformity of particle diameter is also very high simultaneously.
Claims (2)
1. the preparation method of a nano particle scale calibration material is characterized in that adopting the emulsifier-free emulsion polymerization legal system standby, and it specifically may further comprise the steps:
Step 1: polystyrene synthetic
1) cinnamic purifying: styrene is placed separatory funnel, the concentration that adds 0.5～3 times of volume is the washing 2～4 times of fully vibrating of 5% sodium hydroxide solution, keep the upper strata styrene solution, to remove the polymerization inhibitor in the styrene, with distilled water styrene is washed till neutrality again, the NaOH that flush away is residual, then the styrene after will washing places round-bottomed flask to add calcium oxide and removes residual water, styrene is placed dry round-bottomed flask, decompression distillation under the protection of nitrogen, collect the cut under the 0.08MPa, then cut low temperature under the protection of nitrogen of collecting is preserved;
2) synthetic: the 3～6mmol/L lauryl sodium sulfate aqueous solution that in churned mechanically four-hole round-bottomed flask, adds 90～150ml, stir 10～30min, pass into simultaneously the nitrogen deoxygenation, then with reaction unit as in 80～90 ℃ of water-baths, adding 3～5ml is dissolved with the above-mentioned styrene of 0.03～0.15g initator, react and to obtain nattier blue granules of polystyrene emulsion in 4～5 hours, remain nitrogen protection in the course of reaction;
3) separation of product and purification: adding divalence or Tricationic salt demulsifier carry out breakdown of emulsion in the granules of polystyrene emulsion of gained, granules of polystyrene is assembled, emulsion is by the original blue translucent white depositions suspension that become, with discarding supernatant liquor after this suspension centrifugation, can obtain the nano particle of polystyrene; The product of gained is added absolute ethyl alcohol, fully vibration makes its dispersion on the sonic oscillation cleaning machine, and then centrifugation, discards supernatant liquor, so repeatedly clean 2～4 times, the product after cleaning was namely obtained the product of white powder 60 ℃ of oven dry in 12 hours;
Step 2: the screening of nano pipe/polyhenylethylene mono-dispersion microballoon with separate
Adopt the AF2000 MT – Field-Flow Fractionation type field flow separator of German Postnova analytics company, carry out single or the repeated multiple times directly separation of polystyrene microsphere of simple grain, make the following nano particle scale calibration material of 100nm particle diameter; In 80-150ml water or ethanolic solution, be 1ml/min at Tip flow with the 1g sample dissolution, Focus flow is 1ml/min, and Cross flow is each sample introduction 1ml under the condition of 1ml/min; Collect respectively the component of different time sections, and get final product.
2. the preparation method of nano particle scale calibration material according to claim 1, it is characterized in that: described emulsifying agent is lauryl sodium sulfate, dodecyl sodium sulfate or neopelex; Described initator is potassium peroxydisulfate, azo-bis-isobutyrate hydrochloride or azo two isobutyl imidazoline salt hydrochlorates; Described demulsifier is alchlor or changes magnesium or calcium chloride.
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| CN106478857A (en) * | 2016-10-14 | 2017-03-08 | 北京海岸鸿蒙标准物质技术有限责任公司 | For calibrating standard substance of airborne particle counter and preparation method thereof |
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| CN108285506B (en) * | 2018-01-23 | 2020-05-22 | 北京海岸鸿蒙标准物质技术有限责任公司 | Nano particles for polymer turbidity standard substance and preparation method thereof |
| CN111214958A (en) * | 2020-01-17 | 2020-06-02 | 中山大学 | Method for extracting soil rare earth nanoparticles |
| CN112244010A (en) * | 2020-10-26 | 2021-01-22 | 中国农业科学院农业环境与可持续发展研究所 | Temperature response type nanogel, preparation method thereof and preparation method of temperature response type pesticide drug-loading system containing nanogel |
| CN114804212A (en) * | 2022-03-29 | 2022-07-29 | 中山大学 | Preparation method of nano goethite |
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