Utilizing NeSSI™ for Utilizing NeSSI™ for Analytical ApplicationsAnalytical Applications

Dave Veltkamp*Dave Veltkamp*Brian Marquardt*Brian Marquardt*Charlie BranhamCharlie Branham††

*Center for Process Analytical Chemistry (CPAC)*Center for Process Analytical Chemistry (CPAC)University of Washington, Seattle WAUniversity of Washington, Seattle WA

†† Grad Student from Bart Kahr’s group in Chemistry, UWGrad Student from Bart Kahr’s group in Chemistry, UW

CPAC Project OverviewCPAC Project Overview

Goal is to support NeSSI related Goal is to support NeSSI related development within CPACdevelopment within CPAC Developing platforms and demo applicationsDeveloping platforms and demo applications Support PI and student use in research Support PI and student use in research

programs programs

Promote and support wider NeSSI Promote and support wider NeSSI adoption and useadoption and use Web based supportWeb based support Interaction with NeSSI communityInteraction with NeSSI community Legal umbrella for cooperative developmentLegal umbrella for cooperative development

Old NeSSI Gas/Vapor SystemOld NeSSI Gas/Vapor System-NeSSI substrate with 3 MFC’s-2 bubblers for vapor generation

Single inlet line (N2)

Standard Ace Glass impingers

2 MFCs Control N2 flow to bubblers

1 MFC Controls N2 dilution flow

Outlet lineto flow cell

Optical Flow Cell Optical Flow Cell Flow cell is a simple cross Flow cell is a simple cross fittingfitting

6-around-1 fiber optic for 6-around-1 fiber optic for source and collectionsource and collection

Delrin rod with sensing Delrin rod with sensing compound coated on endcompound coated on end

Multiple crosses can be Multiple crosses can be chained together for chained together for screening several screening several compounds at oncecompounds at onceOptical detection using Optical detection using simple reflectance optical simple reflectance optical measurement measurement

Ocean Optics USB2000 VIS Ocean Optics USB2000 VIS spectrometer (350-1000 nm)spectrometer (350-1000 nm)

405 nm blue LED excitation405 nm blue LED excitation Compound fluorescence Compound fluorescence

signal in region 600-900 nmsignal in region 600-900 nm

Vapochromatic ResponseVapochromatic Response

Full spectrum response of the 0%, 10%, and 50% bubbler flow samples used to make the PLS model showing both the change in intensity and shift in peak maximum with changing benzene concentration.

Vapochromic #1 ResponseVapochromic #1 Response

* MFC #3 run at 5% FF rather than 50% FF

Vapochromic #3 ResponseVapochromic #3 Response

Bubbler Results (Benzene Conc.)Bubbler Results (Benzene Conc.)

Benzene concentration (ppm) calculated from the weight loss experiment data as a function of bubbler flow rate (%FF N2)

New Gas Sensor Testing SystemNew Gas Sensor Testing System

More capability to generate analytical vapors, gas blending, and More capability to generate analytical vapors, gas blending, and on-line dilution of vapor streams for method development workon-line dilution of vapor streams for method development work

This system delivered by CORCOR Tech to UM last week and This system delivered by CORCOR Tech to UM last week and will facilitate collaboration with Kent Mannwill facilitate collaboration with Kent Mann

The New CIRCOR NeSSI System The New CIRCOR NeSSI System Has Arrived in MinnesotaHas Arrived in Minnesota

Reconfiguration of CPAC NeSSI™ Reconfiguration of CPAC NeSSI™ SystemSystem

Our Swagelok NeSSI™ system proven to be Our Swagelok NeSSI™ system proven to be very easy to change to suit needsvery easy to change to suit needs Replaced bubblers with permeation tubes and ovenReplaced bubblers with permeation tubes and oven Changed to look at COChanged to look at CO22 in N in N22 blending blending Changed to look at OChanged to look at O22 and moisture in air and moisture in air Investigation of flow, mixing, and dead volumesInvestigation of flow, mixing, and dead volumes

Used to evaluated new analytical instruments in Used to evaluated new analytical instruments in CPAC labCPAC lab ASI microFast GC – 2 column GC with trap injectionASI microFast GC – 2 column GC with trap injection Aspectrics EP-IR mid infrared spectrometer with gas Aspectrics EP-IR mid infrared spectrometer with gas

cellcell

LabVIEW software developed to automate LabVIEW software developed to automate experimentsexperiments

Reconfigured NeSSI™ SystemReconfigured NeSSI™ System

Schematic of SystemSchematic of System

Needed to design system with multiple (3) dilution stagesNeeded to design system with multiple (3) dilution stages Somewhat complex flow paths to minimize dead volumesSomewhat complex flow paths to minimize dead volumes

Had to compromise automated vs. manual control of NHad to compromise automated vs. manual control of N2 2 flows in first two stagesflows in first two stages

Lack of additional MFCs required manual metering valvesLack of additional MFCs required manual metering valves

System FlowsSystem Flows

By closing valves and using the MFCs as flow By closing valves and using the MFCs as flow meters, all flows can be measuredmeters, all flows can be measured

Closing off the NClosing off the N22 flows (SV2 and MFC2) and flows (SV2 and MFC2) and waste valves (PV3 and PV4) allows flow thru waste valves (PV3 and PV4) allows flow thru bubbler to be measuredbubbler to be measured MFC3 and MFC1 set to “valve open” setpointMFC3 and MFC1 set to “valve open” setpoint

All flow streams and legs of system can be All flow streams and legs of system can be flushed by Nflushed by N22

System Flows (cont.)System Flows (cont.)

Dilution FlowsDilution Flows

11stst dilution of bubbler flow at input to MFC 3 dilution of bubbler flow at input to MFC 3 Most of flow goes to waste, MFC setpoint typically 1-5%Most of flow goes to waste, MFC setpoint typically 1-5% NN22 flow regulated by waste needle valve flow regulated by waste needle valve

22ndnd dilution at outlet port of MFC 3 dilution at outlet port of MFC 3 Again most of flow going to waste, MFC 1 set to 1-5%Again most of flow going to waste, MFC 1 set to 1-5% NN22 and 2 and 2ndnd diluted sample flows set by needle valves PV2 and PV4 diluted sample flows set by needle valves PV2 and PV4

33rdrd dilution at output port of MFC 1 dilution at output port of MFC 1 NN22 flow controlled by MFC 2 flow controlled by MFC 2

Important to balance pressures and flowsImportant to balance pressures and flows to avoid to avoid unexpected flow conditions – some tweaking required!!unexpected flow conditions – some tweaking required!!

Aspectrics EP-IR InstrumentAspectrics EP-IR Instrument128 channels from 2.50 to 5.00 microns (4000-2000 cm128 channels from 2.50 to 5.00 microns (4000-2000 cm-1-1))

Each channel approx 19.7 nm wide “band pass”Each channel approx 19.7 nm wide “band pass” Also a 256 channel model availableAlso a 256 channel model available

Runs at an acquisition frequency of 100 scans (rotation) per second

Real-time data collection of fast events High averaging for low LOD applications

Small size and rugged construction Only moving part is the encoder disk Suitable for high vibration process environments No hygroscopic parts

Several optical configuration of sampling cell/accessories possiblePowerful on-line embedded chemometrics software

Aspectrics EP-IR TechnologyAspectrics EP-IR Technology

Aspectrics EP-IR with Gas CellAspectrics EP-IR with Gas Cell

Glow source

Gas cell

Spectrometer

15”

7”

5.2”

ASI microFAST GCASI microFAST GC™™System on loan from ASI as part of WTC project System on loan from ASI as part of WTC project with Infometrixwith InfometrixProgrammed temperature gas chromatograph using Programmed temperature gas chromatograph using

Syringe or valve inlets to a flash evaporator. Syringe or valve inlets to a flash evaporator. Sample delivery to an adsorbent trap for concentrationSample delivery to an adsorbent trap for concentration Desorbtion and delivery to twin capillary columnsDesorbtion and delivery to twin capillary columns Temperature programmed column elutionTemperature programmed column elution Detection by simultaneous flame ionization detectors (FID).Detection by simultaneous flame ionization detectors (FID). Trace levels down to low parts per billion can be measured. Trace levels down to low parts per billion can be measured.

Compact and easy to setup chromatographyCompact and easy to setup chromatography Weight on the order of 12 poundsWeight on the order of 12 pounds Size on the order of a shoe boxSize on the order of a shoe box Speed of analysis on the order of 10 times faster than Speed of analysis on the order of 10 times faster than

competitorscompetitors

Very easy to useVery easy to use Trap injection makes it simple to use and automateTrap injection makes it simple to use and automate Really more like a spectrometer or sensor in operationReally more like a spectrometer or sensor in operation

Even non-chromatographers can use it!!Even non-chromatographers can use it!!

ASI microFAST GCASI microFAST GC™™

Injection

Trap &

Heater external

purge

Injector

vent

vacuum

pump vent

hydrogen

@ 40psi

Restrictor

vent

Heated

Sample Inlet

removable

glass liner

FID

fuel

Injector

Heater

cooling

fan

column

compartment

sheath

Pneumatic Manifold

flowrestrictor

dual columns and heater assembly

FID Air

Back Panel

FID Vents

P

carrier

flow

septa

P P

heated

zone

V3V5V1V8V2

electronic pressure regulators

Fan

V4(n open)

splitter

Ballast

FID Manifold

finger

tight

connections

head of

columns

end of

columns

Vacumn Pump

micromicroFAST GCFAST GC™™ Column Details Column Details

Columnheater

Columnsoven sheath

~1mm ID

column #1100 micron ID

DB-5

column #2100 micron ID

DB-1701

column heater sheath

Columntemperaturesensor

3 meter column length

microFAST GCmicroFAST GC™™ Analytical Cycle Analytical Cycle

Typically 2-3 minutes

Trap pre-purge time

Equilibrate time

Trap preheat timeInjection time

Trap cleanout timeColumn separation time

Trap cool-down timeColumn cool-down time

Sample Time

Adjustable parameters that affect analysis – lots of tuning potential

Interfacing to ASI Interfacing to ASI micromicroFast GCFast GC™™

Example Benzene ChromatogramsExample Benzene Chromatograms

Not very demanding chromatography – but convenient reference method

Experiment: Blending COExperiment: Blending CO22 with N with N22

Goal was to characterize the NeSSI™ system, Goal was to characterize the NeSSI™ system, software control, and the EP-IR gas cell data software control, and the EP-IR gas cell data collectioncollection Series of step changes in MFC setpoints for COSeries of step changes in MFC setpoints for CO22

dilutiondilution Different hold times (delay) between setpoint changesDifferent hold times (delay) between setpoint changes Series repeated 5½ times Series repeated 5½ times

Bubbler replaced with COBubbler replaced with CO22 from tank from tank

Results show very good reproducibility and Results show very good reproducibility and control of the gas blending systemcontrol of the gas blending system Dynamic response consistent with expectationsDynamic response consistent with expectations No dead volume issuesNo dead volume issues

COCO22 Blending Experimental Design Blending Experimental Design

Note: MFC #2 offset by 90%FF, numbers on plot represent step hold time

EP-IR Spectra from COEP-IR Spectra from CO22

ExperimentExperiment

11stst PC of EP-IR Spectra PCA Model PC of EP-IR Spectra PCA Model

Step times and Spectral ResponseStep times and Spectral Response

Note: Total flow = 250 sccm, volume of cell ~ 210 ml – so about 1-2 min exchange time (lag) seems about right

CO2 setpoints inverted & offset for clarity

COCO22 Exp. Cycle Reproducibility Exp. Cycle Reproducibility

22ndnd PC of EP-IR Spectra PCA Model PC of EP-IR Spectra PCA Model

PCA results showing nonlinear PCA results showing nonlinear behavior at high CObehavior at high CO22 conc. conc.

On-line Chemometric Model On-line Chemometric Model ResultsResults

NeSSI™ Permeation TubesNeSSI™ Permeation TubesUsed a stainless steel Used a stainless steel condenser as “oven” for condenser as “oven” for permeation tubespermeation tubes

Removed condenser core and Removed condenser core and replaced with permeation tubesreplaced with permeation tubes

Mounted in single-port ½” Mounted in single-port ½” adapter to direct Nadapter to direct N22 up thru oven up thru oven

Second ¼” adapter block Second ¼” adapter block returns flow into NeSSI™ returns flow into NeSSI™

Temperature maintained by Temperature maintained by flowing water thru jacket from flowing water thru jacket from heater/chillerheater/chiller

Permeation tubes made in-Permeation tubes made in-househouse

Teflon tubing sealed at both Teflon tubing sealed at both endsends

Made different tubes for water, Made different tubes for water, benzene, and toluene vaporsbenzene, and toluene vapors

dil

uti

on

flo

w

Permeation Tube ResultsPermeation Tube ResultsWater permeation tube studyWater permeation tube study

Vapochrome compound (Kafty) Vapochrome compound (Kafty) Oven temp. set at 50Oven temp. set at 50°°C C MFC flow rate set at 10%, 20%, MFC flow rate set at 10%, 20%,

30%, 40%, and 50% for 30 min30%, 40%, and 50% for 30 min Spectra taken at each flow rateSpectra taken at each flow rate

Benzene permeation tube Benzene permeation tube Vapochrome compound (#4) Vapochrome compound (#4) Oven temp. set at 30Oven temp. set at 30°°CC MFC flow rate set at 0%, 10%, MFC flow rate set at 0%, 10%,

20%, 30%, 40%, and 50% for 20%, 30%, 40%, and 50% for 30 min 30 min

Spectra taken at each flow rateSpectra taken at each flow rate

20%

30%

40%

50%

Graph of 10% Subtracted from other spectra

20%

30%

40%

50%

Graph of 10% Subtracted from other spectra

20%30%

40%50%

Graph of 0% Subtracted from other spectra

0%

10%20%30%

40%50%

Graph of 0% Subtracted from other spectra

0%

10%

Conclusions and Future WorkConclusions and Future WorkSetup of NeSSI™ Vapor Platform complete (for now)Setup of NeSSI™ Vapor Platform complete (for now)

LabVIEW software developed and testedLabVIEW software developed and tested Flow dynamics tested and characterizedFlow dynamics tested and characterized New vapor generation ideas to be testedNew vapor generation ideas to be tested

New instrumentation interfaced and testedNew instrumentation interfaced and tested Both Aspectrics EP-IR and ASI microFAST GCBoth Aspectrics EP-IR and ASI microFAST GC™™ valuable valuable

additional tools for monitoring gas mixing and deliveryadditional tools for monitoring gas mixing and delivery Additional applications from Sponsors welcomeAdditional applications from Sponsors welcome

Vapochromic compound testing continuingVapochromic compound testing continuing Moisture, COMoisture, CO22, O, O22 and BTEX sensors testing underway and BTEX sensors testing underway Additional screening and analytical performance testing plannedAdditional screening and analytical performance testing planned

Plan to get back to some microreactor work Plan to get back to some microreactor work Parker NeSSI™ system for reactant and product streamsParker NeSSI™ system for reactant and product streams Microreactor components from Microglass & IMM on handMicroreactor components from Microglass & IMM on hand

Fuel cell studies with Eric Stuve and Chem. E. students Fuel cell studies with Eric Stuve and Chem. E. students plannedplannedWTC Project with Infometrix on Process GC interfaced to WTC Project with Infometrix on Process GC interfaced to NeSSI™NeSSI™