Magnetic agglomeration method for size control in the synthesis of magnetic nanoparticles
View Patent ↗A method for controlling the size of chemically synthesized magnetic nanoparticles that employs magnetic interaction between particles to control particle size and does not rely on conventional kinetic control of the reaction to control particle size. The particles are caused to reversibly agglomerate and precipitate from solution; the size at which this occurs can be well controlled to provide a very narrow particle size distribution. The size of particles is controllable by the size of the surfactant employed in the process; controlling the size of the surfactant allows magnetic control of the agglomeration and precipitation processes. Agglomeration is used to effectively stop particle growth to provide a very narrow range of particle sizes.
1. A method for making magnetic nanoparticles, comprising:
combining a magnetic material precursor and a first surfactant species to form a reaction solution;
reacting the magnetic material precursor at a reaction temperature to form a magnetic particle core at least partially coated with the first surfactant species to form a surfactant-coated magnetic nanoparticle;
growing the surfactant-coated magnetic nanoparticle to a critical size resulting in a critical susceptibility of the surfactant-coated magnetic nanoparticle to produce a critical-sized magnetic nanoparticle capable of spontaneously agglomerating at the reaction temperature;
agglomerating a plurality of the critical-sized magnetic nanoparticles to form agglomerated critical-sized magnetic nanoparticles; and
precipitating the agglomerated critical-sized magnetic nanoparticles to form precipitated magnetic nanoparticles.
2. The method of claim 1 , further comprising extracting the precipitated magnetic nanoparticles.
3. The method of claim 2 , wherein the step of extracting is conducted while continuing at least one of the steps of reacting to form the magnetic particle core and growing the surfactant-coated magnetic nanoparticle to the critical size.
4. The method of claim 1 , further comprising nucleating and growing an additional magnetic particle core during or after agglomerating the plurality of critical-sized magnetic nanoparticles.
5. The method of claim 1 , wherein oxygen is substantially excluded from the reaction solution.
6. The method of claim 1 , further comprising reversing agglomeration of the critical-sized magnetic nanoparticles by exchanging the first surfactant species with a second surfactant species with a greater molecular length than a molecular length of the first surfactant species.
7. The method of claim 1 , wherein the magnetic material precursor is selected from the group consisting of metal carbonyls, metal acetylacetonates, metal acetates, metal alkanoates, metal alkoxides, metal amides, and metal amidates.
8. The method of claim 1 , wherein the magnetic material precursor is iron pentacarbonyl.
9. The method of claim 1 , wherein the magnetic material precursor is iron acetylacetonate.
10. The method of claim 1 , wherein the first surfactant species has a molecular length less than or equal to approximately 20 nanometers.
11. The method of claim 1 , wherein the first surfactant species is selected from the group consisting of alkanes, alkenes, aromatics, alkynes, alcohols, thiols, phosphines, amines, amides, carboxylic acids, phosphonic acids, ketones, aldehydes, esters, diketones, ammonium salts, ethers, polyethers, thioethers, polythioethers, silanes, alkoxy silanes, and silicones.
12. The method of claim 1 , wherein the first surfactant species is selected from the group consisting of 2,4-pentanedione and 3-alkyl-2,4-pentanedione, wherein alkyl comprises between 1 and 18 carbons in an approximately linear chain.
13. The method of claim 1 , wherein the first surfactant species has a molecular length between approximately 0.5 and approximately 20 nm.
14. The method of claim 1 , wherein the precipitated magnetic nanoparticles comprise a magnetic material selected from the group consisting of iron, cobalt, nickel, chromium, manganese, cerium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and magnetic alloys and magnetic compounds thereof.
15. The method of claim 1 , wherein the magnetic material precursor is iron pentacarbonyl and the first surfactant species is 2,4,-pentanedione or 3-decyl 2,4,-pentanedione.
16. The method of claim 1 , wherein the magnetic material precursor is iron acetylacetonate and wherein the first surfactant species is formed by thermal decomposition of acetylacetonate.
17. The method of claim 1 , wherein the first surfactant species is formed by reaction of the magnetic material precursor.
18. The method of claim 1 , wherein the steps of growing, agglomerating, and precipitating are performed in a continuous reaction apparatus configured for extraction of a solid product during a continuous reaction.
19. The method of claim 1 , wherein the steps of growing, agglomerating, and precipitating are performed in a batch reaction apparatus.