Inhibitor Longevity and Deicer Performance Study

Ron Wright - ITDMonty Mills – WSDOT

PNS Pooled Fund Research

PNS Mission Statement

The Pacific Northwest Snowfighters Association strives to serve the

traveling public by evaluating and establishing specifications for

products used in winter maintenance that emphasize

safety, environmental preservation, infrastructure protection, cost-effectiveness and performance.

PNS Targeted Points

SafetySafetyHuman HealthHuman HealthEnvironmental ImpactsEnvironmental ImpactsCorrosionCorrosionAntiAnti--icing and Preicing and Pre--wettingwettingBenefitsBenefits

PNS Targeted Points

PNS has been a recognized pioneer in PNS has been a recognized pioneer in establishing and standardizing chemical establishing and standardizing chemical products for snow and ice control.products for snow and ice control.

Corrosion inhibited products on the QPL Corrosion inhibited products on the QPL are at least 70% less corrosive than are at least 70% less corrosive than straight salt.straight salt.

Current Corrosion PerspectiveProducts are tested to stringent standards in the laboratory. Corrosion inhibited products are less corrosive to mild steel than straight salt.Recommend to wash vehicles on a regular basis to further minimize chemical corrosiveness.

The increased use of deicers has raised concerns about their effects on motor vehicles, transportation infrastructure and the environment. Each year the U.S. and Canada use approximately 20 million tons of deicers and spends 3.3 billion to keep the roads clear of snow and ice.Motorist and trucking associations are conscious of corrosion issues associated with the use of deicers.

Background for Project

Background for ProjectBackground for Project……..On average, deicer corrosion cost per vehicle On average, deicer corrosion cost per vehicle was estimated at $32 per year.was estimated at $32 per year.Deicer salts are known to cause corrosion Deicer salts are known to cause corrosion damage to transportation infrastructure.damage to transportation infrastructure.The cost of installing corrosion protection The cost of installing corrosion protection measures in new bridges and repairing old measures in new bridges and repairing old bridges in the Snowbelt states is estimated bridges in the Snowbelt states is estimated between $250 between $250 -- $650 million annually. $650 million annually. Indirect cost are estimated to be greater than Indirect cost are estimated to be greater than

ten times the cost of corrosion maintenance, ten times the cost of corrosion maintenance, repair and rehabilitationrepair and rehabilitation..

Direct and indirect cost due to corrosion as a Direct and indirect cost due to corrosion as a result of the use of chloride based deicers have result of the use of chloride based deicers have led to the addition of corrosion inhibitors.led to the addition of corrosion inhibitors.

The cost of providing inhibitors in deicing The cost of providing inhibitors in deicing products has resulted in a cost increase of products has resulted in a cost increase of $15 $15 –– 50 dollars per ton.50 dollars per ton.

There are questions about the longevity of There are questions about the longevity of corrosion inhibitors working effectively in the corrosion inhibitors working effectively in the field environment. field environment.

Background for Project…..

Background for Project

Research is needed to investigate whether Research is needed to investigate whether carbohydrates contribute to a carbohydrates contribute to a ““TrueTrue”” freeze freeze point suppression. point suppression.

Research is needed to determine the potential Research is needed to determine the potential benefit of inhibitors for ice melting capacity and benefit of inhibitors for ice melting capacity and the effective working temperature range of the effective working temperature range of products.products.

Research ObjectivesResearch Objectives

The Transportation pooled Funds study aims to The Transportation pooled Funds study aims to answer the following questions:answer the following questions:

What is the longevity of the corrosion inhibitors, What is the longevity of the corrosion inhibitors, when in storage or on the road?when in storage or on the road?

What is the duration the inhibitors remain with the What is the duration the inhibitors remain with the deicers when applied to the road?deicers when applied to the road?

What are the effects of storage (temperatures, UV What are the effects of storage (temperatures, UV intensity, exposure time, and type of deicer) on intensity, exposure time, and type of deicer) on inhibitor longevity and effectiveness? inhibitor longevity and effectiveness?

Research ObjectivesResearch ObjectivesDo the inhibitors contribute to the freezing point Do the inhibitors contribute to the freezing point suppression and/or improve the effectiveness of suppression and/or improve the effectiveness of deicers? deicers?

How does the laboratory test protocol correlate How does the laboratory test protocol correlate with the deicer performance in the field?with the deicer performance in the field?

What is the most effective product to use and its What is the most effective product to use and its optimal application rate to combat ice formation, optimal application rate to combat ice formation, under each typical road weather scenario under each typical road weather scenario identified by the sponsor states?identified by the sponsor states?

Research ObjectivesResearch Objectives

Measure the rate of change in the saltMeasure the rate of change in the salt--sand ratio over time when in storage.sand ratio over time when in storage.Cost EffectivenessCost Effectiveness

Is the inclusion of inhibitors into deicers cost Is the inclusion of inhibitors into deicers cost effective?effective?What is the reasonable duration of protection What is the reasonable duration of protection expected of inhibitors?expected of inhibitors?What is an acceptable level of deicer What is an acceptable level of deicer corrosivity?corrosivity?

Research PlanResearch Plan

Phase One Phase One –– Determine the longevity of Determine the longevity of corrosion inhibitors in storage.corrosion inhibitors in storage.

Liquids in tanks, agitated and nonLiquids in tanks, agitated and non--agitated.agitated.Solids in open piles and covered storage Solids in open piles and covered storage sheds.sheds.

How long does an corrosion inhibitor stay How long does an corrosion inhibitor stay functional after application?functional after application?

For black ice control. For black ice control. During a typical storm event.During a typical storm event.

Research PlanResearch PlanPhase Two Phase Two -- Evaluate the performance Evaluate the performance characteristics of deicers.characteristics of deicers.

Conduct field testing on the following:Conduct field testing on the following:Inhibited and uninhibited products.Inhibited and uninhibited products.Performance Performance ““enhancedenhanced”” products.products.

Research GroupResearch Group

Western Transportation InstituteWestern Transportation InstituteMontana State UniversityMontana State UniversityMSU SubMSU Sub--Zero Research FacilityZero Research FacilityCold Weather Test Bed in Lewistown, Cold Weather Test Bed in Lewistown, Montana (Transcend)Montana (Transcend)

Organization ChartOrganization Chart

Steering CommitteeSteering CommitteeTechnical AdvisorTechnical AdvisorTechnical Advisory CommitteeTechnical Advisory CommitteeChemistry SubChemistry Sub--GroupGroup

WTI Lewistown Cold Regions TestWTI Lewistown Cold Regions Test--bedbed•• Planned infrastructure: asphalt pavement, a weather station, snoPlanned infrastructure: asphalt pavement, a weather station, snowmakers, wmakers,

snowplow, friction testing equipment, and winter maintenance appsnowplow, friction testing equipment, and winter maintenance applicators licators for both liquid and solid productsfor both liquid and solid products

•• Fully operational for winter research during the 2008Fully operational for winter research during the 2008--09 winter season09 winter season

B u i l d i n g

S n o w p r o d u c t i o n

A Cold Region Rural Transportation A Cold Region Rural Transportation Research Test Bed in Lewistown, MTResearch Test Bed in Lewistown, MT

WTI Lewistown Cold Region TestWTI Lewistown Cold Region Test--bedbed

Estimated cost per storm: $20,000 ($6,700 per day)Estimated cost per storm: $20,000 ($6,700 per day)

3 storms targeted for Winter 20083 storms targeted for Winter 2008--20092009

This site has ample space for side by side This site has ample space for side by side comparisons.comparisons.

Task 1Task 1

Experimental design and planning. Experimental design and planning.

Lab investigations will include establishing rapid test Lab investigations will include establishing rapid test methods. methods.

A preliminary understanding of the factors affecting A preliminary understanding of the factors affecting the longevity and performance of corrosion inhibitors the longevity and performance of corrosion inhibitors will be conducted. will be conducted.

The MSU CE Department SubThe MSU CE Department Sub--zero Research Facility zero Research Facility will be utilized for Task 1.will be utilized for Task 1.

The field investigation will run concurrently with the The field investigation will run concurrently with the lab investigation and will validate or supplement the lab investigation and will validate or supplement the lab research findings.lab research findings.

Task 2Task 2

Laboratory investigations began in February, 2008. Laboratory investigations began in February, 2008. Task 2 is broken down into 4 steps:Task 2 is broken down into 4 steps:

1.1. Methods to rapidly quantify chloride and inhibitor Methods to rapidly quantify chloride and inhibitor concentrations.concentrations.

2.2. Methods to rapidly quantify corrosiveness of Methods to rapidly quantify corrosiveness of deicers.deicers.

3.3. Methods to rapidly quantify deicer performance.Methods to rapidly quantify deicer performance.

4.4. Inhibitor longevity under laboratory conditionsInhibitor longevity under laboratory conditions..

Task 2.1. Method to Rapidly Quantify Task 2.1. Method to Rapidly Quantify Chloride ConcentrationChloride Concentration

0

50

100

150

200

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5log [NaCl%]

Ag/A

gCl S

enso

r vs

SCE,

mV

Ag/AgCl sensor #1 vs SCE, mV

Ag/AgCl sensor #2 vs SCE, mV

Task 2.1. Method to Rapidly Quantify Task 2.1. Method to Rapidly Quantify Inhibitor ConcentrationsInhibitor Concentrations

Optical Density via UltravioletOptical Density via Ultraviolet--visible visible spectroscopy (UV/VIS)spectroscopy (UV/VIS)Gas Liquid Chromatography (GLC)Gas Liquid Chromatography (GLC)Gas Chromatography (GC)Gas Chromatography (GC)

Task 2.1. Method to Rapidly Quantify Task 2.1. Method to Rapidly Quantify Inhibitor ConcentrationsInhibitor Concentrations

Task 2.2. Method to Rapidly Quantify Task 2.2. Method to Rapidly Quantify Corrosivity of DeicersCorrosivity of Deicers

Standard curves for each type of deicer: Standard curves for each type of deicer: •• S1: S1: Percent Corrosion Rate (PCR) as a function of the Percent Corrosion Rate (PCR) as a function of the

corrosion potential (corrosion potential (EEcorrcorr)) and the corrosion current and the corrosion current density (density (iicorrcorr))

•• S2: S2: EEcorrcorr and and iicorrcorr as a function of chloride and as a function of chloride and inhibitor concentrationsinhibitor concentrations

Task 2.3. Method to Rapidly Quantify Task 2.3. Method to Rapidly Quantify Deicer PerformanceDeicer Performance

Differential Scanning Calorimetry (DSC) Differential Scanning Calorimetry (DSC) thermograms to identify deicer performance.thermograms to identify deicer performance.

Utilizes a technique that measures the energy Utilizes a technique that measures the energy necessary to maintain a nearnecessary to maintain a near--zero temperature zero temperature difference between the test substance and an difference between the test substance and an inert reference material, with the two materials inert reference material, with the two materials subjected to an identical temperature pattern subjected to an identical temperature pattern (heating, cooling, or constant).(heating, cooling, or constant).

Task 2.3. Method to Rapidly Quantify Task 2.3. Method to Rapidly Quantify Deicer PerformanceDeicer Performance

Differential Scanning Calorimetry (DSC)Differential Scanning Calorimetry (DSC)Provide insight into products freezing/thawing behavior.Provide insight into products freezing/thawing behavior.•• Good indicator of Good indicator of effective temperatureeffective temperature and and iceice--melting melting

capacitycapacity•• DSC thermogram: a reliable DSC thermogram: a reliable QAQA tooltool for deicer productsfor deicer products

Lab experiments with DSCLab experiments with DSC•• Deicers w/ or w/o Deicers w/ or w/o inhibitorsinhibitors: any change in deicing potential?: any change in deicing potential?•• Deicers at various Deicers at various concentrationsconcentrations: best product to use and : best product to use and

optimal application rate for varying field conditionsoptimal application rate for varying field conditions

Correlation with field resultsCorrelation with field results•• DSC a reliable tool to quantify and compare field performance DSC a reliable tool to quantify and compare field performance

of deicer products.of deicer products.

Task 2.3. Method to Rapidly Quantify Task 2.3. Method to Rapidly Quantify Deicer PerformanceDeicer Performance

Task 2.4. Inhibitor Longevity under Lab Task 2.4. Inhibitor Longevity under Lab ConditionsConditions

Utilize the MSU SubUtilize the MSU Sub--Zero Research Facility to Zero Research Facility to research how dilution, UV intensity and duration, research how dilution, UV intensity and duration, temperature, and exposure time affect the temperature, and exposure time affect the longevity and performance of the corrosion longevity and performance of the corrosion inhibitors.inhibitors.

A viable link between inhibitor concentration and A viable link between inhibitor concentration and PCR data will be made.PCR data will be made.

•• Ensure historical PNS corrosion testing and product qualificatioEnsure historical PNS corrosion testing and product qualification n remain viableremain viable

•• Allow for test resultAllow for test result duplication and national recognition of this duplication and national recognition of this research effort andresearch effort and testing procedure testing procedure

Fish Diagram Fish Diagram

Task 3 Field MonitoringTask 3 Field Monitoring1.1. Longevity of the corrosion inhibitor during Longevity of the corrosion inhibitor during

storage.storage.•• Covered and uncovered storage sites for solidsCovered and uncovered storage sites for solids

•• Agitated and nonAgitated and non--agitated storage tanks for liquids 6 agitated storage tanks for liquids 6 total tanks (3 agitated and 3 non agitated).total tanks (3 agitated and 3 non agitated).

2.2. Field Operational TestField Operational Test•• Field trials during 2008 Field trials during 2008 –– 2009.2009.

•• Three artificial storms and one natural.Three artificial storms and one natural.

Field SamplingField Sampling

Products to be evaluatedProducts to be evaluated•• CI liquid MgClCI liquid MgCl22, CI liquid CaCl, CI liquid CaCl22 ,,CI liquid NaCl, and solid CI CI liquid NaCl, and solid CI

NaCl deicers.NaCl deicers.

Meteorological data to be collected with RWISMeteorological data to be collected with RWIS•• Ambient air temperature, precipitation type and amount, water coAmbient air temperature, precipitation type and amount, water content ntent

of the precipitation (snow pack), light intensity including UV sof the precipitation (snow pack), light intensity including UV spectral pectral intensity, duration of sunlight, relative humidity, and wind speintensity, duration of sunlight, relative humidity, and wind speed and ed and directiondirection

•• Pavement TemperaturePavement Temperature: : by RWIS or mobile sensorsby RWIS or mobile sensors

control

EDCBA

…400’ 400’ 400’ 400’

control

EDCBA

…400’ 400’ 400’ 400’

ProgressProgress

Several new personnel have joined the team to assist Several new personnel have joined the team to assist in this project.in this project.Six 3000 gallon poly storage tanks have delivered, set Six 3000 gallon poly storage tanks have delivered, set up and plumbed.up and plumbed.Planning and coordinating with vendors to deliver Planning and coordinating with vendors to deliver product.product.The buildings for two of the pads (solid deicer) began The buildings for two of the pads (solid deicer) began to be constructed in April. to be constructed in April. Necessary information has been obtained from the Necessary information has been obtained from the deicer manufacturers to duplicate or develop methods deicer manufacturers to duplicate or develop methods to rapidly quantify the inhibitor concentration.to rapidly quantify the inhibitor concentration.

Deicer Tanks At LewistownDeicer Tanks At Lewistown

Plastic Lined Gravel PadsPlastic Lined Gravel Pads

This pad will hold 25 tons of salt-sand blend.

Research Time LineResearch Time Line20072007--20092009

Develop methods to quantify deicer Develop methods to quantify deicer performance.performance.

Ice melting, ice penetration and undercutting are not Ice melting, ice penetration and undercutting are not very reproducible and time consuming to run.very reproducible and time consuming to run.Differential scanning calorimetry (DSC)Differential scanning calorimetry (DSC)

Study inhibitor longevity under laboratory Study inhibitor longevity under laboratory conditions.conditions.

MSU SubMSU Sub--zero Research Facilityzero Research FacilityUV intensity and duration, dilution, temperature, and UV intensity and duration, dilution, temperature, and exposure time.exposure time.

Research Time LineResearch Time Line20082008--20102010

Lewistown, Montana Municipal AirportLewistown, Montana Municipal AirportSegment roadway for different products.Segment roadway for different products.Conduct controlled weather events for snow Conduct controlled weather events for snow and black ice.and black ice.Measure chemical parameters, note Measure chemical parameters, note performance characteristics including frictional performance characteristics including frictional data.data.

Submit Research ReportSubmit Research Report

Tasks Milestones 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7 8 9Task 0. Project Management

Project kickoff* Oct-07Task 1. Experiment Design and PlanningTask 2. Laboratory Investigation

Task 2.1. Methods to Rapidly Quantify Chloride and Inhibitor Concentrations

Task 2.2. Method to Rapidly Quantify Corrosivity of Deicers

Task 2.3. Method to Rapidly Quantify Deicer Performance

Task 2.4. Inhibitor Longevity under Laboratory Conditions

Task 3. Field Investigation

Task 3.1. Inhibitor Longevity: Storage Monitoring and Cost-Benefit Analysis

Task 3.2. Deicer Performance: Field Application

Task 4. Project Reporting

Quarterly progress reports End of each quarter

Draft final report Jul-10

Final report w/ executive summary Sep-10

Calendar Year / Month2010200920082007

Project TimelineProject Timeline

ConclusionsConclusions

Answer the big questions?Answer the big questions?Are corrosion inhibitors made to pass the Are corrosion inhibitors made to pass the PNS test or are they really working in the PNS test or are they really working in the field?field?Is laboratory testing data supported by Is laboratory testing data supported by field results?field results?What defines a performance based What defines a performance based product?product?

Potential New SpecificationsPotential New Specifications

Develop new specifications surrounding the Develop new specifications surrounding the longevity of corrosion inhibitors in deicer longevity of corrosion inhibitors in deicer products.products.

Develop new specifications for performance Develop new specifications for performance based deicers. based deicers.

Pacific Northwest SnowfightersPacific Northwest Chemical

Deicer Buyer and User Group

http://www.wsdot.wa.gov/partners/pns/http://www.wsdot.wa.gov/partners/pns/