Brian Marquardt and Dave Veltkamp Applied Physics Laboratory / Center for Process Analytical Chemistry University of Washington Seattle, WA Combining Analytical Sensors and NeSSI to Improve PAT

What is NeSSI™? Industry-driven effort to define and promote a new standardized alternative to sample conditioning systems for analyzers and sensors Standard fluidic interface for modular surface-mount components Standard fluidic interface for modular surface-mount components Standard wiring and communications interfaces Standard wiring and communications interfaces Standard platform for micro analytics Standard platform for micro analytics

NeSSI™ - objectives Facilitate the acceptance / implementation of modular, miniature & smart sample system technology based on ANSI/ISA SP76 standard Provide a technology bridge to the process for...“sensor/lab-on-a-chip” micro-analytical devices Promote the concept of field-mounted (By-Line) smart analytical systems Lay the groundwork for Pipe to Pixel™ open connectivity architecture for intrinsically safe transducer communications and industry standard communication protocols

What does NeSSI™ Provide Simple “Lego-like” assembly Easy to re-configure Easy to re-configure No special tools or skills required No special tools or skills required Standardized flow components “Mix-and-match” compatibility between vendors “Mix-and-match” compatibility between vendors Growing list of components Growing list of components Standardized electrical and communication (Gen II) “Plug-and-play” integration of multiple devices “Plug-and-play” integration of multiple devices Simplified interface for programmatic I/O and control Simplified interface for programmatic I/O and control Advanced analytics (Gen III) Micro-analyzers Micro-analyzers Integrated analysis or “smart” systems Integrated analysis or “smart” systems

Benefits of Being NeSSI™ Your condition space is constrained Volumes, flow rates, pressures, and viscosities inherently bounded by architecture Volumes, flow rates, pressures, and viscosities inherently bounded by architecture Your interfaces are defined Electrical power, communication, and sample are all available in a standard way Electrical power, communication, and sample are all available in a standard way Power budget could be main driver to miniaturize Power budget could be main driver to miniaturize Your sample conditioning can be defined and controlled Specify up-stream and down-stream NeSSI components (and verify) Specify up-stream and down-stream NeSSI components (and verify) All this means your analytical can be more directed and focused

Where Does NeSSI™ Fit in the Lab Instrument/Sensor Interfaces Design standards make development simpler Design standards make development simpler Reduced toolset to be mastered Reduced sample variability to account for Calibration/validation built-in Calibration/validation built-in Consistent physical environment for measurement Stream switching and/or mixing allow generation of standards to match analytical requirements Reaction monitoring Microreactors and continuous flow reactors Microreactors and continuous flow reactors Batch reactors (with fast loop) Batch reactors (with fast loop) Sample Preparation Gas handling (mixing, generation, delivery) Gas handling (mixing, generation, delivery) Liquid handling (mixing, dilution, conditioning, etc.) Liquid handling (mixing, dilution, conditioning, etc.)

NeSSI with an Array of Micro- Analytical Techniques will Impact Many Industries Process Control Process Optimization Product Development

Sensing Technologies Gas Chromatography Thermal Desorption (?) Thermal Desorption (?) Dielectric (√) Spectroscopies IR (+), NIR (+) IR (+), NIR (+) UV- Vis (+) UV- Vis (+) Raman (√) Raman (√) Fluorescence (+) Fluorescence (+) Impedance (+) Conductivity (√) Refractive Index (√) Vapochromic Sensors (+) GLRS (+) Particle Sizing Light scattering (?) Light scattering (?) Turbidity (+) pH (√) RGA (+) Mass Spectrometry (√) LC, SEC, IC (+) Terrahertz (?)

NeSSI™: Enabler for MicroAnalytical (the “rail” concept) Standard Mechanical Interface “Rail” Standard Electrical (Digital) Interface “Rail” Anyone’s Sensor Anyone’s Actuator SAM* Standard “hockey-puckPC” P V *Sensor/Actuator Manager Standard “connectivity ” What technologies are available Suitability for modular sampling systems

Phased Micro Gas Analyzer

Substrate On/Off and Modulating valves Flow Sensor w/ Temp, Pressure w/ Temp Substrate Moisture in Dry Gases PHASED * Micro GC Other Analytical: Ion, Nox. O 2, pH Conductivity, NOx, Turbidity, Density, Opacity Refractive Index, OthersChemometric Sensors for Complex Analytical Measurements. Mod Valve D/A Network Press/ Temp A/D Network *PHASED: Courtesy of Honeywell PHASED microGC

MICRO-GC SLS GCM 5000 < 20 W Power 3 x 2 x 0.6 inches 100 gm / 3 oz.

ABB Natural Gas Chromatograph Analysis section contains stream selection solenoids, pressure regulation, 32 bit digital detector electronics and a dual-train chromatograph in a single, replaceable module (coffee-cup sized) Dimensions: 6.75“ dia. × 16'' long × 9.00'' tall Weight: Approximately 28 lb. (12.7 Kg)

Siemens microSAM GC Valveless live injection with software-adjustable injection volume Maintenance-free column switching and electronic pressure control Accurate measuring results by multiple parallel micro- detectors Can be mounted directly at the sample extraction point because only a single auxiliary gas and very little electrical power is required Simple remote control with Windows-based software and Ethernet communication

Agilent 3000 Micro GC Custom configurations with 1 to 4 replaceable chromatographic channels. Choose from various micro- machined injectors, columns, sample conditioners, and application-specific reports. The modular GC design maximizes uptime, with repair as simple as exchanging one module for another. Increase sensitivity, maintain high precision, remove unwanted contaminants from your sample, or speed up analysis with variable, fixed or backflush injection options. Digital pneumatics control carrier gas flow electronically, enhancing reliability and precision while further simplifying operation. Dimensions: 5.9” x 9.8” x 16.1” Wt: 18 – 37 lbs (portable)

Applied Analytics Inc. Diode Array OMA-300 A Fiber-optics-diode- array process analyzer For on-line concentration monitoring

Applied Analytics Microspec IR FEATURES Ideal for monitoring PPM level WATER in various solvents In stream quantitative measurements Contains no moving parts and Extremely robust allowing for installations in process stream environments Replaces analyzers such as process spectrometers in the process plant.

NeSSI Ballprobe - Raman/NIR/UV

Removable Tip Version Sentelligence Current NIR Sensors Sentelligence Current NIR Sensors - NIR Sensors

NeSSI Compatible Spectroscopic Cell Axiom Analytical, Inc. Currently Available FFV Series Transmission Cells (Near-IR, UV-Visible) FFV Series Transmission Cells (Near-IR, UV-Visible) FNL-120 UV-Visible ATR Cell FNL-120 UV-Visible ATR Cell In Development Raman Cells (Single- and Multi-pass) Raman Cells (Single- and Multi-pass) Possible Development Diffuse Reflectance Cells (For turbid liquids) Diffuse Reflectance Cells (For turbid liquids) Mid-IR ATR Cells Mid-IR ATR Cells Courtesy of Mike Doyle Axiom Analytical, Inc.

NeSSI™ IR Gas Cell

IR Microsystems Microarray 64 Board Dimensions: 66 x 53 mm 2 Board Dimensions: 66 x 53 mm 2 Wilks Enterprise InfraSpec Variable Filter Array

Agilent NeSSI Dielectric Sensor Cable to Agilent Network Analyzer Swagelok 2-Port Valve Base Dielectric Probe Inner Body O-ring (inside) Outer Body Exploded View Close up of Coaxial Probe Tip

Liquid Chromatography for NeSSI™ micromixer diluent in column mobile phase in sample in Scott Gilbert, CPAC Visiting Scholar Crystal Vision Microsystems LLC Atofluidic Technologies, LLC Split flow approach to sampling  -fluidic LC Chip for On-line Sample Pretreatment Pulsed electrochemical detection (on-chip) Liters per minute microliters per minute nanoliters per minute

Aspectrics EP-IR with Gas Cell Glow source Gas cell Spectrometer 15” 7” 5.2”

Interfacing NeSSI™ to ASI microFast GC™ Complete gas/vapor sensing test platform on the bench top Gas delivery, vapor generation, and blending in NeSSI™ Real time verification of composition using GC and EP-IR Easily extended to include other analytical and sample treatments Vapochromic sensor optical cell GC sipper port EP-IR gas cell

NeSSI System for Gas/Vapor Generation and Sensor Calib.

CPAC NeSSI Developments

New Gas Calibration System

Gas Sensor Calibration System

Fringing Field Dielectric NeSSI Sensor Alex Mamishev EE and Brian Marquardt CPAC, UW

NeSSI Raman Sampling Block Reactor NeSSI substrate Sample conditioning to induce backpressure to reduce bubble formation and the heated substrate allows analysis at reactor conditions

PtO 2 NeSSI Sensor Fiber optic cable to Ocean Optics Spectrometer Swagelok 2-Port Valve Base Fiber- optic Probe(405 nm LED) Inner Body O-ring (inside) Outer Body Exploded View Close up of Outer Body Tip VapochromicT ip

Calibrated Gas Generation

Application of Permeation Apparatus

Acknowledgments Center for Process Analytical Chemistry Students – Charles Branham and Wes Thompson, UW Vendors who provided slides Professor Kent Mann, Univ. of Minnesota Scott Gilbert – UW Visiting scholar Swagelok, Parker and Circor ABB, Agilent, Aspectrics, Honeywell, ExxonMobil