Rouge Monitoring

Rouge Monitoring - The Usage of
Science-based Online
Instrumentation to Determine
Derouging and Passivation
Frequency
Nissan Cohen
February 17, 2021
Agenda for Today
Background on Rouge and its Development

Technology of Corrosion Monitoring
Applications of Rouge Monitoring in Pharmaceutical Water Systems
Data examples, charts, and graphs
Comparative Rouge Tests and Observations
Conclusions
Background on Rouge and its Development
Background
Rouging is a thin film, of iron oxide or hydroxide, usually reddish-brown or golden in
color, typically found on stainless steels.
Rouge can also consist of iron, chromium, nickel and other elements.
Rouge is prevalent in the Biotech and Pharmaceutical industry as most systems are
comprised of stainless steel, typically 316/316L grade and the operating temperature
is high.
Rouge normally forms on the interior surfaces of high purity water distillation units,
storage tanks, distribution systems (piping, valves, pump housings, fittings, etc.) and
process vessels.
Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Background
Rouge classifications are Class 1, Class 2 and Class 3
Class1 is non-adherent rouge migratory from another source. Does not affect nor
interact with the surface. Easily removed with wipes
Class 2 – interactive with metal - causes pitting, corrosion, patina (orange, red,
golden). Can only be removed by chemical acids. Forms Hematite
Class 3 – Blue/black, dark purple – is somewhat benign. Can only be etched off
the surface. Reforms rapidly as magnetite.

Rouging of a centrifugal pump housing and impellor

Rouge inside a pipe bore

Vessel spray ball (bagged)

Discoloration on the internal surfaces of a WFI storage vessel
and tank with a spray ball

Rouge discoloration
found on a point of
use 0.45 µm filter
membrane

Rouging on a PTFE
tri-clamp gasket

Background
Many drug manufacturers are concerned about the possibility of
particulate matter contaminating their products and sterile systems.
An effective way to deal with this problem may be to monitor the

rouging rate on-line, in case of process upsets to prevent
contamination.
If Rouge affects the product, the product is deemed unusable.
Rouge rate development is currently unknown

Rouge formulation rate is currently unknown

Background
Depth of rouge to determine passivation frequency is

unknown – Unless a coupon system was devised with the
installation of the water system and subsequent analysis was
instituted, or a section of pipe is physically removed.
Coupon systems have been devised but are rarely checked or

extracted, as the complete shutdown of the water system is
needed.
Derouging and Passivation frequencies are determined by

discoloration or a time interval determined by “QC
queasiness”

Industry Needs
Method to determine Rouge formulation rates
Method to determine Rouge thickness
Scientific method to determine derouging frequency
Scientific method to determine frequency for derouging and

passivation
On-line method which integrates with existing instrumentation,

network, data logging, and computer systems
Easily calibration and maintenance

Rouge Monitoring
Rouge is a form of corrosion.
Corrosion is an electrochemical phenomenon based on electron migration with a

combination of OH-.
Corrosion can be determined by measuring the current and potential across anode
and cathode poles

Technology of Corrosion Monitoring
Corrosion Reaction
2 Fe + 2 H2O + O2 2 Fe ++ 4OH - 2 Fe (OH)2
-
OH OH
-
-
OH
-
OH
- - - -
OH OH OH OH
H2O O2 H2O
2+ 2+
Fe
e- Fe
e-
2 Fe
I
2 Fe ++ +4e 2 H 2O + O -
2 +4e 4OH-
corr
Anodic Reaction Cathodic Reaction

Figure from essay WFI SYSTEMS WITH SUPPLEMENTAL MONITORING SYSTEM FOR QUALITY CONTROL IN CONNECTION WITH ROUGING (G. Henkel,
B. Henkel, Essay No 71 / Rev. 00, 2007)

Figure from essay WFI SYSTEMS WITH SUPPLEMENTAL MONITORING SYSTEM FOR QUALITY CONTROL IN CONNECTION WITH ROUGING (G. Henkel,
B. Henkel, Essay No 71 / Rev. 00, 2007)

Stern and Geary Equation
E ba bc
= = Rp
imeas ( 2.303 icorr )(ba + bc )
Where:
i meas ba = Anodic Tafel Slope
bc = Cathodic Tafel Slope
2ΔE

Applications of Rouge Monitoring in
Pharmaceutical Water Systems
Derouging and Passivation
Shutdown: minimum 3-4 days, often longer

Chemical costs – citric acid, nitric acids, phosphoric acids, etc.
Disposal costs – of chemicals acid waste neutralization using caustics:

NaOH, NH4OH etc.
Labor costs – manpower

Production shutdown
Frequency: Every 6 months, every quarter, annually, every 18 months,

biannually? How is this determined?

Costs for Derouging and Passivation of a USP Purified system feeding a
WFI still and WFI system
Feed Water
USP Purified Water Loop
Distillation
Unit
WFI or
Hot
Water pump
Storage
Tank
Points of
Return line Use

Costs for Derouging and Passivation of a USP Purified system
feeding a WFI still and WFI system
76 LPM (20 GPM) USP Purified Water, 15 LPM (4 GPM) distillation unit, 38 LPM
(10 GPM) WFI with Storage, 50mm (2”) piping loop, 300 meters (1000‘) of piping
$30,000 includes chemicals and labor only
Plus: downtime of production in days, client’s labor, non-production of products

over the days time period.
Totals: $50,000 and higher

SCADA,
Modbus BMS,
TCP/IP DELTA V
ETC.
The Rouge Monitor consists of a high sensitivity front end probe/wireless transmitter, a 3 year duration
battery, and as a stand-alone unit connected to a communication gateway.
The probe/transmitter assembly performs various functions including the integration of the probe data,
supply of VDC power to the probes, calculation of the rouge rate and rouge accumulation, and transmission
of parametric data to a gateway. The WirelessHART uses spread spectrum frequency hopping 2.4GHz radios.
These radios communicate directly with the gateway or through other transmitters forming a mesh network.
The gateway polls up to 100 remote Rouge Monitor units in the field. The gateway uses Modbus TCP/IP
communication to transmit all data from remote wireless RM units to a DCS, SCADA, BMS, or process control
system.

Feed Water
USP Purified Water Loop
Distillation
Unit
WFI or
Hot
Water
pump
Storage
Tank
Points of
Use
Return
line SCA
Modbu
DAKnowledge
Connecting Pharmaceutical ISPE.org/singapore-affiliate
s
Fitting is for a probe to measure steam condensate. An 1” spirax steam trap is connected to1.5” fitting with drain stubs. Length of stubs
(TYPICAL) to accommodate typical valve with outlet to typical Swagelok compression ferule fittings with drain tubes.

Data examples, charts, and graphs
50 10
Rouge Monitor Tag 6170 - Conductivity 0.7 µS/cm
45 9
Integrated Rouge Rate or Metal Loss (nanometers)

40 8
35
(nanometers/month) 7
30 6
25 5
Rouge Rate
20 4
15 3
10 2
5 1
0 0
8-Jan 15-Jan 22-Jan 29-Jan 5-Feb 12-Feb 19-Feb 26-Feb 5-Mar 12-Mar 19-Mar 26-Mar

Rouge Monitor Tag 6170 - Conductivity 0.7 µS/cm
10
(nanometers/month)
14
9
12 8
7
10
6
Rouge Rate
8
5
6 4
3
4
2
1
0 0
16-Feb 23-Feb

Data and Inferences
Data is single digit nanogram/L levels =15 - 40Å

Real-time changes in the rouge rate are due to POU usage, flow rates,
temperature fluctuations, and operational characteristics of the water
system
To understand if rouge is in product, need to measure at extremely small

levels
Accumulation rates over time are easily interpreted
Alarm limits for control can be set at very low levels
Scientific assessment for derouging and passivation

Comparative Rouge Tests and Observations
Procedure for Auger Electron Spectroscopy
Spool pieces from the sample company’s piping system were removed and sent to a
laboratory to perform Auger (aw-jay`) Electron Spectroscopy. This electron
spectroscopy measures the depth of rouge development on the surface of the spool
piece.
This test was initiated to show an independent measurement of rouge and to compare
the measurement to an On-line Rouge Monitor’s readings over the same time period.
Different water systems were sampled with different pharmaceutical water

classifications. This was to investigate if variances, in water classification and
temperature, would cause undue variances in the readings of the On-line Rouge
Monitor.

Rouge Accumulation
On-line Auger Electron Rouge Rouge Meter
TIME Rouge Spectroscopy Meter Variance in
Monitor Measurement Variance
Reading Nanometer (nm)
Angstroms (Å)
Company A 0.70  0.75  - 6.6% 50 nm
11 Months 500 Å
Company B 0.075  0.080  - 6.2% 5 nm

10 Months 50 Å
Company C 0.17  0.16  +5.9% 10 nm

10 Months 100 Å

Water System Descriptions
Company A is a purified water system maintained at 80° C for 8 hours and cooled to 40°
C each day.
High corrosion rates occurred in the system, as it is not well maintained.

Deposition in system, results in slightly lower monitor readings than tested results.
Company B is Hot WFI system with central water system supply
Very low corrosion rates typical of many hot systems
Company C is Hot WFI system from midsize process plant
Typical to Median corrosion rates for hot systems with older piping systems

Observations and Results
Operating temperatures, ramp up temperatures, and pharmaceutical water classification had
no influence on the comparability of the two different methods to determine rouge
accumulation.
Variances between two completely different methods to determine rouge accumulation over
time were quite small. In the very small measurements of Company B and Company C,
differences were 50 Å and 100 Å or 5 nm and 10 nm, respectively.
Although the variance is displayed in percentages between the two measurements, the actual
measurement differential is infinitesimal.
Auger Electron Spectroscopy can be used as an independent method to verify the accuracy of
the On-line Rouge Monitor.

Conclusions
Conclusions
On-line determination of rouge development, rouge thickness without sampling, labor and
laboratory testing is inexpensive, dynamic, and integratible to existing computer and networking
schemes.
Passivation and repassivation frequencies based on science and need. Not QC queasiness.
Rouge Monitoring Units are inexpensive: saving one passivation annually will pay for the unit
many times over.
Cost savings: Tens of Thousands to Hundreds of Thousands of dollars per year per site.
Installation of units is based on number of loops with risk-based management and

assessments.

Questions and Comments?
Nissan Cohen
Biopharmaceutical Water Doc
Biopharmwaterdoc.com
nissan@biopharmwaterdoc.com

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Rouge Monitoring - The Usage of

Background on Rouge and its Development

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Rouge classifications are Class 1, Class 2 and Class 3

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

An effective way to deal with this problem may be to monitor the

If Rouge affects the product, the product is deemed unusable.

Rouge rate development is currently unknown

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Depth of rouge to determine passivation frequency is

Coupon systems have been devised but are rarely checked or

Derouging and Passivation frequencies are determined by

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Method to determine Rouge thickness

Scientific method to determine derouging frequency

Scientific method to determine frequency for derouging and

On-line method which integrates with existing instrumentation,

Easily calibration and maintenance

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Corrosion is an electrochemical phenomenon based on electron migration with a

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Shutdown: minimum 3-4 days, often longer

Disposal costs – of chemicals acid waste neutralization using caustics:

Labor costs – manpower

Frequency: Every 6 months, every quarter, annually, every 18 months,

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

USP Purified Water Loop

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

$30,000 includes chemicals and labor only

Plus: downtime of production in days, client’s labor, non-production of products

Totals: $50,000 and higher

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

USP Purified Water Loop

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Integrated Rouge Rate or Metal Loss (nanometers)

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Data is single digit nanogram/L levels =15 - 40Å

To understand if rouge is in product, need to measure at extremely small

Accumulation rates over time are easily interpreted

Alarm limits for control can be set at very low levels

Scientific assessment for derouging and passivation

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Different water systems were sampled with different pharmaceutical water

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

Company B 0.075  0.080  - 6.2% 5 nm

Company C 0.17  0.16  +5.9% 10 nm

Connecting Pharmaceutical Knowledge ISPE.org/singapore-affiliate

High corrosion rates occurred in the system, as it is not well maintained.

Company B is Hot WFI system with central water system supply

Very low corrosion rates typical of many hot systems

Company C is Hot WFI system from midsize process plant