Synthesis, Characterization, and Isolation of Metal Precursor Inks

Transcription

1 Synthesis, Characterization, and Isolation of Metal Precursor Inks Khushbu Zope, Chaitanya Mahajan, Scott Williams, Denis Cormier, Bruce E. Kahn AMPrint Center at Rochester Institute of Technology

2 AMPrint RIT Dr. Denis Cormier Director AMPrint Center Rochester Institute of Technology 160 Lomb Memorial Dr. drceie@rit.edu (585) Dr. Bruce E. Kahn Chief Scientist and Director of Business Development AMPrint Center Rochester Institute of Technology 160 Lomb Memorial Dr. Bruce.Kahn@rit.edu (585)

3 AMPrint Center Mission To be a focal point for functional printing research and development. To catalyze the growth of the functional printing industry To develop new functionally printed materials, processes, and products 3

4 AMPrint Center Facility ~$4.5M for construction covering ~6,000 square feet $4.5M additive manufacturing and 3D printing equipment 4

5 AMPrint Center World First! Metallojet ( Metal Inkjet ) Al & Alloys Wire feed < 200 µm resolution 1 lb./hr. deposition rate Depending on resolution Vader Systems, Buffalo, NY 5

6 AMPrint Center World First! 24 x 24 in single pass Solid ink, UV photopolymer Expansion for 2 more inks Metal Post processing Photonic Curing Chip shooter Sensor Films, Inc. Rochester, NY Xerox Rochester, NY 6

7 AMPrint Center World First! Hybrid metal additive manufacturing (additive + subtractive) 5 axis CNC machine with laser cladding head Dual powder feeders Allows alternate deposition (additive) and finishing (subtractive) of machine metal materials Graded compositions Hardinge, Elmira, NY 7

8 AMPrint Center World First! 3D Printed Lattice Guitar Body Bob Sneider Professional Guitar Player Professor, Eastman School of Music 8

9 Students Khushbu Zope Chaitanya Mahajan 9

10 10 Outline Introduction Types of Metal Inks S-Ag MOD complex Cu MOD Future Work Optomec Aerosol Jet Copper ink 20 μm line width 10

11 11 Outline Introduction Types of Metal Inks S-Ag MOD complex Cu MOD Future Work 11

12 12 Functional Printing Techniques Aerosol jet Line width: ~15 μm Ink viscosity: 1000 cp Nozzle dia.: μm Inkjet Line width: ~30 μm Ink viscosity: 10 cp Nozzle dia.: 25 μm Microextrusion Line width: ~70 μm Ink viscosity: 1M cp Nozzle dia.: μm 12

13 13 Outline Introduction Types of Metal Inks S-Ag MOD complex Cu MOD Future Work 13

14 14 Types of Metal Inks Nanoparticle Ink MOD Ink Nanoparticle Ink Nanoparticles in suspension Sintering of nanoparticles High processing temperature High solid loading MOD Ink Metal salt solution Reduction of metal compounds Low processing temperature Low solid loading 14

15 15 Alternate Approach: Photonic Curing Rapid curing/sintering of high temperature printed materials on temperature sensitive surfaces High power Xenon flash lamps Pulse length: >250 μsec Sintering on large area K. A. Schroder,

16 16 Outline Introduction Types of Metal Inks S-Ag MOD complex Cu MOD Future Work 16

17 Isolated MOD complex 1. Solid complex 2. High throughput curing conditions MOD Ink Why? Improved stability Optimum organic content Ready to use Proposed structure of Solid Silver complex (S-Ag) Silver Oxalate : 71 % mass of silver Thermally decompose to Ag and CO 2 Ethylene diamine : Low boiling point (116 C) Two binding sites 17

18 S-Ag Complex: Synthesis Ag O O O O Ag H 2 N Water, Ice bath NH 2 H N H H H N Ag O O O O Ag H N N H Precipitate in isopropyl alcohol S-Ag structure H H S-Ag HOOC-COOH + AgNO 3 AgOOC-COOAg + HNO 3 Stored below 4 C in dark 18

19 S-Ag complex: Thermal decomposition Thermogravimetric analysis of S-Ag Complex H N H H H N Ag O O O O Ag H N N H + + Ag NH 3 CO 2 + H 2 O H H 47 % w/w Ag heating rate = 5 C/min 19

20 Curing conditions Differential thermal analysis (DTA) - Thermogravimetric analysis (TGA) of ink Curing conditions Heating rate = 2 C/min Last endothermic peak at 121 C (A)before curing, (B)120 C for 3 minutes, (C)150 C for 1 minute and (D)90 C for 1 minute, then at 120 C for 3 minutes. 20

21 21 Ag MOD Ink for Inkjet Printing Ag ink [3] : S-Ag Complex + water + isopropyl alcohol Surface tension = 29 mn/m Viscosity = 15 cp Resistivity = 27 µω cm Printing technique: Dimatix DMP 3000, 20 µm drop spacing Observations: [3] Khushbu Zope, Thesis (2017), RIT Ag MOD ink for inkjet printing Hot plate curing: 90 C for 1 minute, then 120 C for 3 minutes. Printing without nozzle clogging Film thickness: ~ 3 µm Stable ink when stored below 4 C Ink rheology can be modified for other printing process 1270 dpi image Before curing Printing and curing of Ag ink 500 nm Surface characteristics for Ag sample After curing 21

22 Characterization: Silver MOD IJ Prints Bulk Resistivity (Ω cm) Bulk Resistivity vs Curing Time 9.E-05 8.E-05 7.E-05 6.E-05 5.E-05 4.E-05 3.E-05 2.E-05 1.E-05 0.E Curing Time (min) Film thickness: µm Isolated complex % Area of holes in the printed film 3.1% 2.1% PET 22

23 Outline Introduction Types of Metal Inks S-Ag MOD complex Cu MOD Future Work 23

24 Cu MOD Ink for IJ & AJ Printing (a) (b) (c) Cu ink [4] : Surface tension = 30 mn/m Viscosity = 12 cp Resistivity: 100 µω cm Printing technique: Optomec aerosol jet Cu formate 1 Butanol 2-amino-2-methyl-1-propanol Diethylene glycol methyl ether Observations: Uniform line with less overspray using low atomizer flow (Figure a) Line width (L w ): ~20 µm Line thickness: 2-3 µm As the sheath gas flow increases, overspray increases (Figure b) [4]. Farraj et al. (2015), Chemical communications L w =20.5 µm L w =12.5 µm Aerosol jet prints 24

25 Cu Ink Curing % Weight % Temperature ( C) Thermogravimetric analysis of Cu MOD ink 200 um 20 µm line 10 um Ink was cured using pulsed photonic curing Good adhesion to Kapton 5 um Surface characteristics for AJ printed Cu sample 25

26 Cu Ink Curing Copper 2 um 10 um Kapton Observation: Raised areas suggestive of entrapped volatile material Cross section view of IJ printed cured Cu ink on Kapton 26

27 27 Outline Introduction Types of Metal Inks S-Ag MOD complex Cu MOD Future Work 27

28 Future Work Formulate inks with higher solid loading Sinter inks to achieve conductivity closer to that of the bulk metal Develop functional inks to fabricate thermistors, displays, heaters, PZT actuators etc. 28

29 Acknowledgements National Institute On Deafness and Other Communication Disorders of the National Institutes of Health under Award Number R01DC The AMPrint Center is a NY Center for Advanced Technology (CAT) and is supported by the New York State Foundation for Science, Technology and Innovation (NYSTAR). 29

30 Ag Complex and Printed Film Characterization

31 S-Ag complex: Characterization 1556->1552 υ as (O C O) 1375->1355 υ s (C C) 1300->1294 υ s (C O) 771->754 δ as (O C O) υ s (Ag O) 410->340 υ (Ag O) Infra-red Spectroscopy (A) (B) Journal of Analytical and Applied Pyrolysis 2016, 120, Journal of Physical Chemistry 1957, 61 (7),

32 Film Characterization: X-Ray Diffraction Crystalline FCC 32

33 Film Characterization: EDS 33