MPWT19-14325

How we learn from our history in the development of the next generation of linings

Michael Harrison
Sherwin-Williams Protective & Marine Coatings
Tower Works, Kestor Street , Bolton, BL2 2AL
United Kingdom

ABSTRACT

The market for protective linings in the oil and gas sector has evolved in the last 30 years, reflecting on
both increased performance demands and productivity demands. This paper will review the successes
seen with tank linings and the changes seen within the market (legislative, HSE and more aggressive
conditions), later, via a case study it will elaborate how these have steered R&D in the development of
the next generation of high-performance linings.

Finally, the relevance of the American Petroleum Guidance (API652 and 653) to establish their
continued relevance in lining selection and inspection intervals will be reviewed along with the utilization
of linings to support changing demands (increased life expectancy and inspection intervals).

Keywords: Inspection, High-Performance Linings, Life Expectancy, Legislation, Durability, Flexibility,

Performance Testing, Novolac, Abrasion, Next Generation
 INTRODUCTION

The market for protective linings in the oil and gas market has changed considerably in the last 30 years
with increasing crude temperatures (and higher sulphur content), demand for longer life/increased
inspection intervals, simpler applications as well as the advent of biofuels (alcohols and biodiesel as
fuels). Alongside these performance changes, there are a lot of tanks requiring maintenance where
simple linings during new construction may no longer be appropriate or even allowed with new HSE and
other legislative changes.

This paper intends to give a brief history of the market, identifying key issues, then to review what has
worked in the past and how this can be taken into the development of new linings. A case study in the
development of a next-generation lining will be used to describe how history and changes in the market
demands are taken into account.

As API 652 and 653 are globally accepted guidances for lining selection and inspection, we will review
their continued relevance and how these next-generation linings can support lining selection and assist
in inspection (ease of cleaning, increased inspection intervals etc.)

HISTORY OF LININGS IN PROTECTIVE AND MARINE

There have been significant changes in the requirements of linings for storage and processing of
chemicals, particularly in the Oil and Gas Market – these can be summarised in the following table.
Linings have had to be developed to meet the current and future demands in the linings and other
corrosive areas in the Protective and Marine market.
 TIMELINE TECHNOLOGY COMMENTS
Pre 1980 Coal Tar Epoxies 1st listed as a carcinogen in US – 1980.
Used in crude and water immersion.

Pre 1980 Thin Film Epoxies Ambient crude and while oils.
Low solids and multiple coats required.
Pre 1980 Reinforced Lining Schemes (Epoxies Refurbishment and long life expectancy
and Polyesters) schemes. High cost complex application.
1980’s 1st Generation Solvent Free Epoxies Ambient crude and while oils, poor
application properties
1980’s Glass Flake Vinyl Esters Only option for high temperature and
pressures seen in process vessels.
Became prevalent when CO2 floods
were causing issues. VOC and HSE
issues have haunted Vinyl Ester
Technology.
nd
1990’s 2 Generation Solvent Free Epoxies Crude oil, refined petrochemicals – first
linings to offer “proven” long life for new
construction and maintenance.
1990’s 1st Generation Epoxy Phenolic Medium solids high temperature and
Novolac's pressure linings
1990’s 1st Generation Solvent Free Epoxy Plural and single leg applied linings for
Phenolics higher temperature service.
2000 MIL PRF 23236 introduced Edge retentive coatings and optical
requirements to ensure longer life bleach inspection methods introduced,
from linings and easier inspection.
2000’s Solvent ree Epoxies for Ballast and 1st use of solvent free linings in US Navy
Navy Fuel in MIL PRF 23236 – exclusive use of solvent free linings in
2004.
2000- First fast return to service solvent free Proven long life for these schemes since
2010’s epoxy and Epoxy Novolac linings launch – edge retention and optical
introduced to the market. inspection techniques standard on high
performance linings.
Table 1. History of Chemical Resistant Linings

The company has been at the forefront of linings development and were amongst the 1st companies to
introduce solvent free epoxy linings to the market as well as being pioneers in fast return to service
linings and styrene free vinyl ester technology.

DEVELOPMENT OF REQUIREMENTS IN THE LININGS MARKET (OIL AND GAS)

In the early days, crude oil and heavy fuel oils were considered to be non-corrosive – this theory was
not borne out in practice as water and acid contamination lead to severe corrosion and “pitted” bottoms.

As the market has developed (advances in technology, greater understanding of the chemistry as well
as changes in legislation) so have the requirements from linings.

There is an increased understanding of the characteristics required of a lining in both new construction
and maintenance. Solvent free and edge retentive linings have demonstrated superior performance
which, coupled with enhanced flexibility, have given proven long life expectancy.
Proof of performance for ultra-high solids
(UHS) / solvent free linings

Figure 1
10 Year inspection:

20-30 mils (500-750µm) lining thickness

remaining (no observable loss)

Ease of cleaning allows for improved

inspection.

Only slight corrosion identified due to

mechanical damage of the lining.

Adhesion values of ~ 2200psi (15MPa)

Tank returned to service with anticipated

additional 20 years lifetime.

Figure 2
 MID-LATE 20TH CENTURY 2010’S
Crude oil – Heated for loading and unloading. Shale oil and higher temperature / acidity crudes.

Storage of simple refined petrochemicals. Biodiesel (vegetable oil based) – alcohol and acid
content a concern.
Tanks often unlined as the corrosive nature of Bioethanol
crude and refined petrochemicals
underestimated.
Fuel additives including oxygenates (ethers Unleaded gasoline is more aggressive to linings and
etc.) fuel dyes, antioxidants etc. have mild steel tanks due to alcohol content.
changed the effect the fuel has on linings and
steel. Many of the additives are diluted with
Methanol which in turn makes the fuel much
more aggressive and damaging to traditional
linings.
Purity requirements for aviation fuels: Mil P 23236,
Def Stan 80-97 & EI Standard 1541
High sulphur crudes – amine scrubbers.

Increased volume of crude oil transported by rail.

Performance of quality linings confirmed as the

tanks come out of service.
Table 2. Changes In Performance Requirements

CHANGES IN PERFORMANCE REQUIREMENTS

The American Petroleum Institute (API) give guidance on construction, protection and inspection of
above ground steel storage tanks:

1. API 650 offers guidance on tank construction

2. API 651 has suggestions on use of cathodic protection
3. API652 reviews the types and selection of linings for protection of storage tanks
4. API653 gives direction on inspection intervals and how linings can assist increase these

API 652 gives guidance on the selection of linings and some direction on the type of linings (it leaves
the exact selection in the hands of the lining supplier as it appreciates that generic linings may not
perform the same) based on the following criteria:

1. Condition of substrate
2. Tank history (repairs, subsidence, previous cargo)
3. Stored material (Temperature, Approvals, Purity, flexibility)
4. Durability

API 652 also stresses the importance of surface preparation and application in ensuring the performance
of high performance linings. Quality linings suppliers offer high levels of inspection during application to
help ensure the optimum performance of the lining.
 EXAMPLES FROM THE API GENERIC CATEGORIES (BY THICKNESS)

Thin Film (<500µm) Thick Film (>500µm) Thick Film Reinforced

Traditional Solvented Epoxy Solvent Free Epoxies Solvent Free Epoxies

High Temperature Phenolic Solvent Free Epoxy Phenolic Solvent Free Epoxy Phenolic

Solvent Free Epoxies Glass Flake Vinyl Ester Reinforced Novolacs

Solvent Free Epoxy Phenolic

Table 3 – API Lining Categories

There are of course many variants in these categories in terms of performance and application
characteristics.

API 653 gives guidance (and reasons for) on inspections of bulk storage tanks:

1. Initial Inspection Interval (6.4.2.1) shall not exceed 10 Years unless the criteria in the table below
are met: (Table 6.1)
2. No specific statement on thick film linings as such

Tank Safeguard Add to initial Interval

Fibreglass reinforced lining as per API 652 5 Years

Thin film lining as per API 652 2 Years

Release prevention barrier as per API 650 Annex 1 10 Years

Soil side cathodic protection 5 years

Table 4 – API Suggested Inspection Intervals

Subsequent inspections are determined in accordance with a risk based inspection protocol based on
measured corrosion rate – meeting all the criteria can increase the maximum interval to 15 years.
 DESIGN CHARACTERISTICS FOR THE NEXT GENERATION OF LININGS

The company has had considerable success in the linings market (particularly in oil, gas and marine
markets) and in the design of the next generation of linings it has been important to review what the
key features have been so these could be incorporated. The following were identified at the outset:

REQUIRED FEATURE HOW THIS HAS BEEN DELIVERED FUTURE DEMAND

Flexibility optimised
Flexibility
Extended resistance: more
Long service life Chemical Resistance
aggressive solvents and higher
Edge Retention
temperatures / pressures
OAP Inspection
OAP* Inspection Edge retention
Ease of inspection
Edge retention Ease of cleaning
Abrasion resistant
Plural application short pot-life
Fast return to service Fast return to service with single
chemistry
leg application
Ease of application Formulated for single leg
Table 5: Identified Requirements for Next Generation of Linings

*Optically Active Pigments as recommended by US Navy (MIL PRF 23236)

CASE STUDY IN THE DEVELOPMENT OF NEXT GENERATION LININGS

At every stage of the development, focus is given to meeting the required characteristics so that the
next generation lining would deliver the requirements of the market, while maintaining all the attributes
established over many years of supplying linings.

The route followed in lining development was as follows:

1. Polymer (Resin) system optimised for chemical resistance without compromising on flexibility (a
key requirement for long lining life), pot-life or cure time.
2. Pigmentation selected to ensure chemical resistance and barrier properties. Advanced
technology utilised to “bind” the pigments into the resin which enhances performance, reinforcing
the film, whilst maintaining the viscosity required for all common application methods (airless,
plural and others).
3. Aluminum oxide incorporated to enhance abrasion resistance
4. PTFE included to optimise cleaning properties without impacting adhesion to steel or overcoating
properties
5. The thixotrope used in development was balanced to maintain excellent application properties
(over a range of film thicknesses) and edge retention.
6. Optically active pigmentation was incorporated to assist with inspection (reducing the reliance
on high voltage spark testing)

All of these were finely balanced to ensure the performance and application of characteristics. At all
stages, a key competitive lining was included to ensure we were ahead of the current materials in the
market.
 PERFORMANCE TESTING (SUMMARY APPENDED)

Test type Completed tests

Application and inspection 1. Airless spray (low ratio)
2. Plural airless
3. OAP demonstration
Mechanical properties 1. Hardness
2. Adhesion to steel
3. Adhesion to self
4. Impact
5. Flexibility
6. Abrasion
7. Edge retention
Isothermal immersion testing ISO 2812 – for approvals and chemical resistance
guide – there is significant 3rd party testing ongoing.
Auto-clave testing 3rd party testing in hydrocarbon, water and sour gas
blends
Table 6: Performance Testing

CONTINUED RELEVANCE OF API 652 AND 653 WITH NEXT GENERATION OF LININGS

Correct selection of and application of lining for the service conditions (and substrate condition) as per
API 652 remain vital to ensuring the life of storage tanks. Significant experience from lining suppliers
(based on real proven track records) have given an understanding of why linings last, which has
enabled long life expectancy to be built into the next generation of linings (flexibility, permeability etc.).
Inspection of storage tanks will continue to be a requirement to ensure optimal lifespan. Linings can be
used to simplify this procedure:

1. Abrasion-resistance and easy cleaning, enhancing the emptying, cleaning and inspection
process – ease of cleaning (and reduced damage) has been reported to offer significant time
and money savings over the life of the tank.

2. Optical bleach enhancements not only offers benefits during application (the lining can be
checked for pin-holes during application) – the use of UV lamps during planned inspections will
identify any damage (the optical bleach maintains its activity during service) to the lining which
may not be visible to the naked eye, especially when spark testing after service is not a
recommended practice.

3. New in-situ methods are becoming available, which allow for quicker predictive inspection of
storage tanks to be completed. These next-generation linings are designed to be compatible
with such inspection techniques. These methods are becoming accepted as API 653 compliant
and, combined with long life linings, offer potentially huge savings in inspection costs over the
projected life of a tank.
 CONCLUSIONS
To meet the demands of the market it was necessary to combine Novolac Chemistry with binding
technology (barrier properties, performance, cure and normal airless application). This new technology
enables normal airless application in a single or multi-coat system from 15 - 50 mils [375-1250 microns].

This improved application does not come with a drop in performance as the next generation linings
maintain resistance to aggressive chemicals at high temperatures and pressures. Resistance to other
aggressive materials becoming more common in 21st-century tanks (bio-fuels, ethanol, methanol etc.)
has also been achieved. With its superior performance, combined with high end-use versatility, next-
generation linings can reduce complexity for owners and specifiers.

There are not only time savings in application and cure as initial and future inspection times may also
be reduced using the OAP technology, with holidays and missed areas identified and rectified
immediately during application. The ultra-high solids (UHS) technology and capability to be applied over
a wide range of thicknesses (15-50 mils [375-1250µm]) makes this lining suitable for new construction
and maintenance projects, where application over pitted surfaces is a requirement.

Formulation using abrasion-resistant pigmentation and PTFE – allows for easy cleaning of the lining (the
low surface tension) without risk of abrasive damage. This enhanced cleaning capability offers
substantial benefits to the owner/operator as, in many cases, cleaning costs, in a maintenance
turnaround, can be significant. PTFE is thermally and chemically inert (and is evenly dispersed
throughout the entire film) ensuring cleaning properties are maintained throughout the life of the lining.

API 652 and API 653 remain the key lining selection and inspection standards in the market. The lining
selection criteria in API 652 remains valid with the next generation of linings.

As part of the development, it has been important to keep up to date on the latest inspection techniques
in the market – on this basis compatibility with the latest “in-situ” inspection techniques (which are in-
line with API 653) has been a key function of these next generation linings. This combination of lining
and state of the art inspection can offer potentially huge savings over the life of the tank.
 ACKNOWLEDGEMENTS

Paula Donadio Sherwin-Williams PCG Technical Protective and Marine

Selwyn Williams Sherwin-Williams Senior R&D Group Leader
Bruce Toews Sherwin Global Oil and Gas Marketing Director
Amal Al-Borno Charter Coatings

REFERENCES

1. ASTM(1) G 8 (latest revision), “Standard Test Methods for Cathodic Disbonding of Pipeline Coatings”
2. ASTM(1) D 4541 (latest revision), “Standard Test Method for Pull-Off Strength of Coatings Using
Portable Adhesion Testers”
3. ASTM(1) D 2240 (latest revision), “Standard Test Method for Rubber Property—Durometer
Hardness”
4. ASTM(1) D 4060 (latest revision), “Standard Test Method for Abrasion Resistance of Organic
Coatings by the Taber Abraser”
5. ASTM(1) D 2794 (latest revision), “Standard Test Method for Resistance of Organic Coatings to the
Effects of Rapid Deformation (Impact)”
6. ASTM(1) D 1331 (latest revision), “Standard Test Methods for Surface and Interfacial Tension of
Solutions of Paints, Solvents, Solutions of Surface-Active Agents, and Related Materials”
7. NACE(2) RP0394 : “Application, Performance, and Quality Control of Plant-Applied Single Layer
Fusion-Bonded Epoxy External Pipe Coating”
8. NACE(2) SP 188: “Discontinuity (Holiday) Testing of New Protective Coatings on Conductive
Substrates”
9. NACE(2) TM 0185: “Evaluation of Internal Plastic Coatings for Corrosion Control of Tubular Goods
by Autoclave Testing”
10. ISO (3) 4624 (latest revision): “Paints and varnishes -- Pull-off test for adhesion”
11. ISO (3) 2812 (latest revision): “Determination of resistance to liquids”
12. API 652(4): “Linings of Aboveground Petroleum Storage Tank Bottoms”
13. API 653(4): “Tank Inspection, Repair, Alteration, and Reconstruction”

(1) ASTM International, 100 Barr Harbor Dr., West Conshohocken, PA 19428-2959.
(2) NACE International, NACE International Headquarters: 15835 Park Ten Place, Houston, Texas 77084, USA
(3) ISO Central Secretariat Chemin de Blandonnet 8, CP 401 - 1214 Vernier, Geneva, Switzerland
(4) API, 200 Massachusetts Avenue NW, Suite 1100, Washington, DC 20001-5571, USA
 OVERVIEW OF KEY PERFORMANCE TESTING

Test Standard employed Test conditions Scheme evaluated Results Comments

API recommended
API Compliant N/A 20 mils (500µm)
Practice 652 rev.4
ISO 4624 / ASTM >3031 psi
Adhesion As per standard 20 mils (500µm)
4541 (20MPa)
Hardness ASTM D2240-05 Shore D 20 mils (500µm) >75
Cathodic Disbondment ASTM G8 As per standard 20 mils (500µm) Average 3mm
Taber Abrasion ASTM D4060 CS17 Wheel / 1000g 20 mils (500µm) 51mg/1000 cycles
ASTM D1331–14 Demonstrates
Surface Tension 41.8 (dynes/cm)
Method D ease of cleaning
ASTM D2794 -
Direct Impact 7 days cure 20 mils (500µm) 25 inch lb
Impact
ASTM D2794 -
Reverse Impact 7 days cure 20 mils (500µm) 8 inch lb
Impact
Dry Heat ASTM D2485 7 days cure 20 mils (500µm) Underway
NACE RP0394,
Appendix H,
Flexibility As per standard 20 mils (500µm) 2.3%
Procedure B shall be
performed
Thick Film cracking NACE TM0304 NACE TM0304 Underway
Edge Retention MIL PRF 23236 20 mils (500µm) >70% retention
Holiday Testing NACE SP 188 100 volts per mil (25µm) 20 mils (500µm) Pass
Airless Spray, Plural Closed film at <8 mils (200µm), Excellent
Application
Airless Sag >50 mils (1250µm) application
 OVERVIEW OF KEY PERFORMANCE TESTING

Test Standard Employed Test Conditions Scheme Evaluated Results Comments

No blistering, severe
discoloration was
Pressure: observed in the Equivalent
500 psi/35.5 bar; hydrocarbon phase. Post
Temperature: 275F/135C Test Pull-Off Adhesion performance to a
Gas Phase: after 14 days: competitor control
15 MPa. (Retained 85%
5% H2S, 5% CO2, and 90% CH4.
of Initial Value).
Hydrocarbon phase: 1:1 No blistering, severe
Autoclave Exposure NACE TM 0185 Toluene/Kerosene 20 mils (500µm) discoloration was
Aqueous Phase: observed in the
1% NaCl. hydrocarbon phase. Post Alternative lab
Decompression: Test Pull-Off Adhesion
after 14 days: selected to ensure
Cool down to room temperature
and then release pressure in one
Vapour: 1183psi uniform results.
Hydrocarbon: 1793psi
(1) hour.
Aqueous: 2583psi
Initial: 1923-2388 psi
Isothermal Immersion ASTM D6943 Methanol at ambient No visible Control failed after
20 mils (500µm)
deterioration 7 days
Isothermal Immersion ASTM D6943 Ethanol at 122°F (50°C) Slight Control failed after
20 mils (500µm)
discoloration only 15 days
Isothermal Immersion ASTM D6943 5% NaCl in DI Water Moderate surface
20 mils (500µm)
discoloration only
Isothermal Immersion ASTM D6943 5% NaCl in Tap Water Severe surface Control failed in
20 mils (500µm)
discoloration only less than 6 months
Isothermal Immersion ASTM D6943 Sour Crude Oil at 275°F Moderate surface
20 mils (500µm)
(149°C) discoloration only
Isothermal Immersion ASTM D6943 Sour Crude Oil + 5% Moderate surface
NaCl in Tap Water at 20 mils (500µm) discoloration only
210°F (99°C)
 OVERVIEW OF KEY PERFORMANCE TESTING

SALT WATER IMMERSION AT 210°F (99°C)

Next Generation Single Leg Epoxy Novolac,

SALT WATER IMMERSION AT 210°F (99°C)

Competitive 1st Generation Epoxy Phenolic

Lining (used as control) – Failed in 6 months

IMMERSION IN METHANOL at 77°F (25°C)

>6 months in Methanol– no visual degradation

IMMERSION IN METHANOL

Competitors control Sample 7 days in

Methanol at 77°F – Blistering
 OVERVIEW OF KEY PERFORMANCE TESTING

AUTOCLAVE EXPOSURE NACE TM 0185

No blistering or swelling were observed in any

phase of all three samples. ➢ Moderate
discoloration was observed in the gas and
hydrocarbon phases of all three samples.

Pull-off Adhesion (Two Weeks after

Download):
• Gas Phase ‒ 1183 psi (8 MPa)
(90% Adhesive and 10% Cohesive Failure)
• Hydrocarbon Phase ‒ 1793 psi (12
MPa)
(100% Adhesive Failure)
• Aqueous Phase – 2583 psi (18MPa)
(100% Cohesive failure)
Pressure: 500 psi/35.5 bar;
Temperature: 275°F/135°C
Gas Phase: 5% H2S, 5% CO2, 90% CH4
Hydrocarbon phase: 1:1 Toluene/Kerosene
Aqueous Phase: 1% NaCl.
Decompression: Cool down to room temperature and
then release pressure in one (1) hour.

OPTICALLY ACTIVE PIGMENT

Successful trial application demonstrating the

OAP visual identification of holidays during
application.:

“This new solution will allow us to use less

material and get tanks shipped out faster
due to the additional OAP color option and
fast dry. It sprays just like our absolute
favorite product to spray.”

EDGE RETENTION