Methods of making ferrite nanocrystals
Methods of making iron-based ferrite nanocrystals are provided. In such methods the ferrite may include iron oxides and iron/cobalt or iron/manganese mixed salts. The method may include thermal decomposition of one or more precursors of the ferrite, consisting of an organic salt of the metal or metals constituting the ferrite of interest, comprising the operation of heating a solution comprising said precursor(s) in the presence of a surfactant and of a non-aqueous organic solvent comprising an ether, at temperature sufficient to cause thermal decomposition of said precursor, wherein the solvent may further comprise a saturated or unsaturated, linear or branched aliphatic hydrocarbon, liquid at temperatures above 45° C. and having a boiling point above the boiling point of the ethereal solvent.
1. A method of making iron-based ferrite nanocrystals comprising
selecting one or more iron-based ferrite precursors
heating a solution consisting essentially of said one or more precursors, a ligand, and at least two organic solvents to a temperature sufficient to cause thermal decomposition of said one or more precursors,
wherein the iron-based ferrite is selected from the group consisting of iron oxides, mixed oxides of iron/cobalt, iron/manganese and any combination thereof,
wherein the ligand is selected from the group consisting of: saturated or unsaturated aliphatic acids and aliphatic amines, and
wherein one of the at least two organic solvents comprises an ether and another of the at least two organic solvents comprises a linear or branched saturated aliphatic hydrocarbon having from 18 to 36 carbon atoms, said saturated aliphatic solvent being liquid at room temperature and having a boiling point above 298° C. and higher than the boiling point of the ether solvent.
2. The method of claim 1 , wherein the aliphatic hydrocarbon comprises squalane.
3. The method of claim 1 , wherein at least one of the two solvents is diphenyl ether or dibenzyl ether and wherein the volume ratio between said solvent of ether and said aliphatic hydrocarbon is less than 80%.
4. The method of claim 1 , wherein the ligand is selected from the group consisting of a carboxylic acid and an aliphatic amine having an aliphatic chain from 10 to 18 carbon atoms.
5. The method of claim 1 , wherein the ligand comprises oleic acid or decanoic acid.
6. The method of claim 1 , wherein the precursor comprises Fe(III) acetylacetonate.
7. The method of claim 1 , wherein the molar ratio of precursor to ligand is between 1:3 and 1:7.
8. The method of claim 1 comprising an initial step of degassing at subatmospheric pressure at a temperature lower than 120° C.
9. The method of claim 1 , wherein heating is carried out at the reflux temperature of the solution.
10. The method of claim 8 , wherein said degassing step is followed by a heating step at an intermediate temperature lower than 240° C., after which said temperature is maintained for a time between about 10 minutes and about 5 hours, and wherein the solution is heated in a final step to the reflux temperature, at atmospheric pressure.
11. The method of claim 10 , wherein the heating of said solution, from the intermediate temperature to the reflux temperature, is performed by applying a thermal gradient of constant heating between 1° C./min and 7° C./min.
12. The method of claim 1 wherein the nanocrystals obtained by said method are transferred in an aqueous solution by a ligand exchange process comprising introducing into the solution, a ligand comprising a di- or multihydroxy head group for anchoring to the nanocrystal and a polyoxyalkylene tail soluble in polar solvents to be injected during a post-reflux cooling phase when the temperature reaches values lower than 120° C.
13. The method of claim 12 , wherein the ligand used in the ligand exchange process is a compound derived from gallic acid, connected to a chain of polyethylene glycol via a covalent ester bond.