Microfluidic chemical reactor for the manufacture of chemically-produced nanoparticles

• US 20050129580A1
• Filed: 02/26/2004
• Published: 06/16/2005
• Est. Priority Date: 02/26/2003
• Status: Abandoned Application

• Current Assignee: Lake Shore Cryotronics, Inc.
• Original Assignee: Lake Shore Cryotronics, Inc.
• Inventors: McGee, Christopher, Pollard, Kimberly, Swinehart, Philip R., Dharmatilleke, Saman
• Application Number:
  US10/788,967
• Publication Number:
  US 20050129580A1
• Time in Patent Office: Days
• US Class Current: 422/100
• CPC Class Codes: B01F 25/3142 the conduit having a plurality of openings in the axial direction or in the circumferential direction
• CPC Class Codes: B01F 25/31421 the conduit being porous
• CPC Class Codes: B01F 25/431 Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
• CPC Class Codes: B01F 25/432 with means for dividing the material flow into separate sub-flows and for repositioning and recombining these sub-flows; Cross-mixing, e.g. conducting the outer layer of the material nearer to the axis of the tube or vice-versa
• CPC Class Codes: B01F 25/4321 the subflows consisting of at least two flat layers which are recombined, e.g. using means having restriction or expansion zones
• CPC Class Codes: B01F 25/433 Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
• CPC Class Codes: B01F 25/4333 Mixers with scallop-shaped tubes or surfaces facing each other
• CPC Class Codes: B01F 33/30 Micromixers
• CPC Class Codes: B01F 33/3012 Interdigital streams, e.g. lamellae
• CPC Class Codes: B01F 33/3033 using heat to mix or move the fluids
• CPC Class Codes: B01J 19/0093 Microreactors, e.g. miniaturised or microfabricated reactors laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027
• CPC Class Codes: B01J 2219/00783 Laminate assemblies, i.e. the reactor comprising a stack of plates
• CPC Class Codes: B01J 2219/00828 Silicon wafers or plates
• CPC Class Codes: B01J 2219/00831 Glass
• CPC Class Codes: B01J 2219/00837 comprising coatings other than catalytically active coatings
• CPC Class Codes: B01J 2219/0086 Dimensions of the flow channels
• CPC Class Codes: B01J 2219/00873 Heat exchange
• CPC Class Codes: B01J 2219/00889 Mixing micromixers B01F33/30
• CPC Class Codes: B01J 2219/00907 using membranes
• CPC Class Codes: B01J 2219/00932 Sonic or ultrasonic vibrations
• CPC Class Codes: B01J 2219/00936 : UV-radiations
• CPC Class Codes: B01J 2219/00943 : Visible light, e.g. sunlight
• CPC Class Codes: B01J 2219/00945 : Infrared light
• CPC Class Codes: B01J 2219/0095 : Control aspects
• CPC Class Codes: B01J 2219/00952 : Sensing operations
• CPC Class Codes: B01J 2219/00959 : Flow
• CPC Class Codes: B01J 2219/00961 : Temperature
• CPC Class Codes: B01J 2219/00963 : Pressure
• CPC Class Codes: B01J 2219/00966 : pH
• CPC Class Codes: B01J 2219/00972 : Visible light
• CPC Class Codes: B01J 2219/00977 : Infrared light
• CPC Class Codes: B01L 2200/147 : Employing temperature sensors
• CPC Class Codes: B01L 2300/044 : pierceable, e.g. films, membranes
• CPC Class Codes: B01L 2300/0654 : Lenses; Optical fibres
• CPC Class Codes: B01L 2300/0816 : Cards, e.g. flat sample carriers usually with flow in two horizontal directions
• CPC Class Codes: B01L 2300/0864 : comprising only one inlet and multiple receiving wells, e.g. for separation, splitting
• CPC Class Codes: B01L 2300/0867 : Multiple inlets and one sample wells, e.g. mixing, dilution
• CPC Class Codes: B01L 2300/0887 : Laminated structure
• CPC Class Codes: B01L 2300/0896 : Nanoscaled
• CPC Class Codes: B01L 2300/1805 : Conductive heating, heat from thermostatted solids is conducted to receptacles, e.g. heating plates, blocks
• CPC Class Codes: B01L 3/06 : Crystallising dishes
• CPC Class Codes: B01L 3/5027 : by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip B01L3/5023 takes precedence; micromixers B01F33/30; microreactors for synthesis B01J19/0093; microcapillary devices in general B81B1/00
• CPC Class Codes: B01L 3/502753 : characterised by bulk separation arrangements on lab-on-a-chip devices, e.g. for filtration or centrifugation separation in general B01D; microapparatus for analysis using electrophoresis G01N27/44791; sample preparation G01N1/28
• CPC Class Codes: B01L 7/00 : Heating or cooling apparatus autoclaves B01J3/04; Heat insulating devices
• CPC Class Codes: B82Y 30/00 : Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C30B 29/605 : Products containing multiple oriented crystallites, e.g. columnar crystallites
• CPC Class Codes: C30B 7/00 : Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions from molten solvents C30B9/00; by normal or gradient freezing C30B11/00; under a protective fluid C30B27/00

Abstract

The present invention discloses microfluidic modules for making nanocrystalline materials in a continuous flow process. The microfluidic modules include one or more flow path with mixing structures and one or more controlled heat exchangers to process the nanocrystalline materials and reagents in the flow path. The microfluidic modules can be interconnected to form microfluidic reactors that incorporate one or more process functions such as nucleation, growth, and purification.

Claims

1. A microfluidic module comprising:

a flow path comprised of a channel formed in a first substrate and enclosed by a second substrate, the flow path having a fluid inlet and a fluid outlet;

mixing structures in the flow path; and

one or more independently controlled heat exchangers in thermal contact with the flow path for conditioning a nanocrystal forming reagent within the flow path;

the flow path inlet receives the nanocrystal forming reagent and conditioned nanocrystal forming reagent is removed from the flow path at the outlet, the flow path inlet and outlet capable of forming a fluid tight seal with one or more controlled fluid delivery devices.

2. The microfluidic module of claim 1 having multiple flow paths.

3. The microfluidic module of claim 1 further wherein the heat exchanger includes an optical source of energy.

4. The microfluidic module of claim 1 wherein the flow path further includes sensors chosen from the group consisting of:

particle size sensor, pressure, flow, reagent chemical composition sensing, the sensor output used as an input to a controller for open or closed loop control or said microfluidic module.

5. A microfluidic module of claim 1 wherein the controlled heat exchanger includes a temperature sensor, a heat exchanger, and a controller.

6. The microfluidic module of claim 1 wherein one or more of the independently controlled heat exchangers thermally preconditions the nanocrystal forming reagent.

7. The microfluidic module of claim 1 wherein the first substrate includes one or more thermal isolation structures whereby the flow path is separated into one or more thermally isolated sections.

8. The microfluidic module of claim 1 wherein one or more additional ports are provided at intervals along the flow path for the purpose of adding reagents to modify the shapes, surface coating, and/or sizes of the growing nanocrystals, the one or more ports located between the inlet and outlet of the flow path and capable of forming a fluid tight seal with one or more controlled fluid delivery devices.

9. The microfluidic module of claim 1 wherein the mixing structure mixes multiple flow streams uniformly by dividing the flow stream into multiple smaller streams, the smaller streams being mixed and reacted and recombined with the aid of mixing and thermal equalization structures internal to the flow path or paths.

10. The microfluidic module of claim 1 wherein said flow path includes a particle size sensor wherein fluorescent emission from said particles is utilized in open or closed loop control of temperature or fluid flow in the flow path.

11. The microfluidic module of claim 1 wherein the flow path includes a nucleation section whereby nucleation of nanocrystals occurs during a flow process, said nucleation section including a nucleation length of channel in the flow path, said one or more heat exchangers maintaining said nucleation section at a nucleation temperature, the nucleation section having an inlet in the flow path for receiving a one or more nanocrystal nuclei-forming reagent fluids and an outlet in the flow path for removing nucleated nanocrystals from the nucleation section.

12. The microfluidic module of claim 1 wherein the flow path includes a growth section whereby growth of nanocrystals and/or nucleated nanocrystals nuclei or nanocrystals occurs during a flow process, said growth section including a growth length of channel in the flow path, one or more ports for adding nanocrystal forming reagents, said one or more a heat exchangers maintaining the growth section at a growth temperature, the growth section having an inlet in the flow path for receiving a nanocrystal forming reagent fluid, and an outlet in the flow path for removing nanocrystals from the growth section.

13. The microfluidic module of claim 1 wherein the flow path includes a growth termination section in which growth of nanocrystals is terminated during a flow process, said growth termination section including a growth length of channel in the flow path, said one or more heat exchangers maintaining the growth termination section at a growth termination temperature, the growth termination section having an inlet in the flow path for receiving nanocrystals in a reagent and an outlet in the flow path for removing nanocrystals from the growth termination section.

14. The microfluidic module of claim 1 wherein the flow path further comprises a purification section whereby phase separation or exchange of fluids containing nanocrystals from fluids occurs during a flow process, said purification section including a separation device in a length of channel in the flow path, said one or more heat exchangers maintaining the purification section at a purification temperature, the purification section having an inlet in the flow path for receiving nanocrystals in a reagent and an outlet in the flow path for removing nanocrystals from the purification section.

15. The microfluidic module of claim 1 wherein the flow path includes a coating section in which a coating is formed on a stabilized nanocrystal in a flow process, said coating section including a heat exchanger for maintaining the coating section at a coating temperature, at least one coating section inlet in the flow path for receiving nanocrystals and coating forming reagent, and at least one coating section outlet in the flow path for removing coated nanocrystals from the coating section, the growth section inlet and outlet capable of forming a fluid tight seal with one or more controlled fluid delivery devices.

16. The microfluidic module of claim 1 comprising one or more sections chosen from the group consisting of nucleation, growth, growth termination, purification, and combinations of these in the flow path on a substrate.

17. A microfluidic module comprising:

a first flow path comprised of a channel formed in a first substrate and enclosed by a second substrate, the first flow path having a fluid inlet and a fluid outlet;

a separation device in the flow path for removing impurities from nanocrystals in a fluid, the first flow path inlet receiving nanocrystals in a fluid, said separation device removing impurities from the nanocrystals in the fluid and the first flow path outlet for removing the nanocrystals from the flow path, the flow path inlet and outlet capable of forming a fluid tight seal with one or more controlled fluid delivery devices; and

a port in the first flow path.

18. The microfluidic module of claim 17 wherein the separation device includes a porous membrane through which the nanocrystals are prevented from passing and fluids are allowed or caused to be exchanged by cross-flow, counter-flow, or co-flow from a second fluid path separated from said first flow path by said membranes.

19. The microfluidic module of claim 17 wherein the separation device includes a porous membrane having pores in said membrane that permit the passage of dispersed nanocrystals.

20. The microfluidic module of claim 17 wherein the separation device contains a semiconductor membrane with internal pore dimensions modulated in order to cause nanoparticles to pass through by means of a drift ratchet property.

21. The microfluidic module of claim 17 wherein the separation device contains membranes that can be caused to be hydrophilic or hydrophobic by means of the application of a voltage.

22. The microfluidic module of claim 17 wherein the separation device includes a porous membrane made from semiconductors, silica glass, metal oxides or polymers.

23. The microfluidic module of claim 17 wherein the separation device includes a porous membrane and the first flow path is in fluid communication through the membrane with a second flow path, said second flow path having an inlet and an outlet, wherein the second flow path contains a device to pulse the pressure of the fluid in the first flow path.

24. The microfluidic module of claim 17 wherein the separation device contains a piezoelectric, magnetic or optical means of inducing sonic or ultrasonic waves in the first flow path for the purpose of separately manipulating nanocrystals in the fluid.

25. The microfluidic module of claim 17 wherein the separation device includes a porous membrane and the first flow path is in fluid communication through the membrane with a second flow path, said second flow path having an inlet and an outlet.

26. A microfluidic reactor comprising:

a flow path including one or more fluidly connected microfluidic modules for making nanocrystals in a flow process, the flow path in each module is a channel formed in at least a first substrate and enclosed by at least a second substrate, said channel in thermal contact with one or more independently controlled heat exchangers along the flow path for conditioning a nanocrystal forming reagent fluid in the flow path, each module having an at least one inlet in the flow path for receiving the reagent fluid and and least one outlet in the flow path for removing conditioned reagent fluid from the module, each said inlet and outlet capable of forming a fluid tight seal with one or more fluid delivery devices.

27. The microfluidic reactor of claim 26 comprising one or more flow paths.

28. The microfluidic reactor of claim 26 comprising microfluidic modules with one or more inlets, outlets, or combinations of these.

29. The microfluidic reactor of claim 26 wherein the modules are connected in a manner to include parallel, series, or a combination of these.

30. The microfluidic reactor of claim 26 wherein a microfluidic module includes a reagent preconditioning section, a nucleation section, a growth section, and a growth termination section.

31. The microfluidic reactor of claim 26 wherein the channel flow path includes a mixing structure.

32. A method of making nanocrystals comprising:

conditioning nanocrystal forming reagents in a flow path, said flow path including one or more fluidly connected microfluidic modules for making nanocrystal product in a flow process, the flow path in each module is a channel formed in a first substrate, said channel in thermal contact with one or more independently controlled heat exchangers and mixing structures along the flow path to condition the nanocrystal forming reagents in the flow path;

each module having an inlet in the flow path for receiving the nanocrystal forming reagent fluid and an outlet in the flow path for removing conditioned reagent fluid from the module, each said inlet and outlet capable of forming a fluid tight seal with one or more controlled fluid delivery devices; and

monitoring a detectable property of said nanocrystal product or reagent in a portion of the flow path and adjusting a controllable heat exchanger, a fluid delivery device, reaction time, or a combination of these to maintain the detectable property of the nanocrystal product in a pre-determined range.

33. The method of claim 32 wherein the nanocrystals forming reagents are fluorescent nanocrystal forming reagents.

34. The method of claim 32 wherein the mixing structures within the flow path divide and recombine the fluid flow of the nanocrystal forming reagents.

35. The method of claim 32 further including the act of purifying the conditioned nanocrystal forming reagents in the flow path.

36. The method of claim 32 comprising one or more flow paths.

37. A method of purifying nanocrystals comprising:

providing nanocrystals in a fluid into the flow path of a microfluidic module having a separation device in the flow path of said microfluidic module, and

separating an impurity from said nanocrystals within said microfluidic module.

38. The method of claim 37 wherein the impurity is a coordinating ligand, a solvent, nanocrystal forming reagents, particles, and combinations of these.

39. The method of claim 37 further comprising the act of providing a second fluid to the flow path from one or more ports along the flow path.

40. The method of claim 37 the separated impurity is a first ligand attached to the nanocrystals that is exchanged for a second ligand to be attached to the nanocrystals in the fluid.