Presentation given at the IM Oilfield Minerals & Markets Forum Houston 2018 on raw materials for oilfield well cements covering demand, challenges and opportunities.

1. OILFIELD WELL CEMENTS
Raw Material Demand, Challenges and Opportunities
Claudio Manissero
President, ChemCognition LLC
IM Oilfield Minerals and Markets
Forum
May 7, 2018

2. Well Completion Cements
• Cementing is a critical step in well completion
• Main purposes of cementing
− Zone isolation and segregation
− Stability of formation
− Corrosion control
− Improvement of pipe strength
• Efficacy of cementing dependent on chemistries (cement mix components and additives),
mix water (amount and impurities), environment (temperature and pressures), slurrying
(slurrying equipment, physical properties – fluidity, segregation, etc.)
• With changes in the drilling strategies, cementing chemistries have been undergoing
changes in formulation to compensate for the wider variety of temperatures and pressures.
• Main component of oilfield cement is a Portland type cement. Additives are added to the
cement slurry to : 1) disperse cement particles, 2) modify the setting time, 3) control loss of
the liquid (mainly water) from the cement slurry during and after placement, 4) compensate
for shrinkage of the cement, 5) improve interfacial bonding between cement and casing,
6) control influx and migration of well fluids in the cement

3. API Cement Classes
• Class A: For use from surface to 6000 ft (1830 m) depth*, when special properties are not required.
• Class B: For use from surface to 6000 ft (1830) depth, when conditions require moderate to high sulfate resistance.
• Class C: For use from surface to 6000 ft (1830 m) depth, when conditions require high early strength.
• Class D: For use from 6000 ft to 10,000 ft depth (1830 m to 3050 m), under conditions of high temperatures and
pressures.
• Class E: For use from 10,000 ft to 14,000 ft depth (3050 m to 4270 m), under conditions of high temperature and
pressures.
• Class F: For use from 10,000 ft to 16,000 ft depth (3050 m to 4880 m), under conditions of extremely high
temperatures and pressures.
• Class G: Intended for use as a basic cement from surface to 8000 ft (2440 m) depth. Can be used with accelerators
and retarders to cover a wide range of well depths and temperatures.
• Class H: A basic cement for use from surface to 8000 ft (2440 m) depth as manufactured. Can be used with
accelerators and retarders to cover a wider range of well depths and temperatures.
• Class J: Intended for use as manufactured from 12,000 ft to 16,000 ft (3600 m to 4880 m) depth under conditions of
extremely high temperatures and pressures. It can be used with accelerators and retarders to cover a range of well
depths and temperatures.
The majority of cement used in Oilfield is Type H & G (80% of usage) – rest is spread out among
different types with Class A and C comprising bulk of remainder.

4. Properties To be Controlled
Use, location, environmental factors (temperature, pressure) and specific well design
require that oilfield cements address a number of factors by additives used to modify
the cement binder(s) used:
• Density
• Early and long term strength
• Flexural strength
• Permeability
• Shrinkage and compensation
• Bonding
• Flexibility
• Pumpability
• Segregation

5. Raw Materials Used
• Cement
• Heavy weight additives (to increase slurry density)
− Barite
− Hematite
− Ilmenite
− Sand
• Light weight additives/extenders (to decrease slurry density)
− Bentonite
− Diatomaceous earth
− Pozzolans
− Chemicals (Sodium silicate)
• Non-Mineral additives/admixtures
− Accelerators – Sodium-Chloride, Calcium chloride
− Accelerators – Chloride free calcium nitrate/sodium thiocyanate (new)
− Retarders – lignosulfonates, cellulose derivatives, hydroxycarboxylic acids
− Fluid Loss Additives – HEC, polymers
− Loss Circulation Additives – Gilsonite, ground coal, ground walnut shells, fibers (inert polymers and
natural)
− Expansion additives – calcium sulfoaluminate, calcium oxide, magnesium oxide
− Dispersants – polynaphthalene sulphonate (SNS)
− Antifoaming agents – polyglycols, silicones

6. CHALLENGES WITH CEMENT
• Change in ASTM cement definition – increase in limestone content
− Change in strength gain
− Addition of pozzolans
• New air regulations for cement manufacturers
− Rationalization of capacity in US (a number of plants shut down)
− Implementation of new scrubbing technologies (residuals in cement)
− Changes in raw materials and fuel
• Strong market demand driven by economy
− Supply tightness
− Higher level of imports
− Unwillingness to make “special grades” focus on contruction
− Higher pricing
• Effect On Oilfield cement?
− Unknown effects on formulations
− Harder to get desired type
− Price increases

7. CHALLENGES WITH POZZOLANS
• Environmental Regulations for Power Plants affecting Fly Ash
− Shutting down coal fired plants switching to natural gas
− Implementing scrubbing technologies that affect properties of materials
− Managing sources of coals to minimize emissions – changing fly ash
chemistries that are untested.
− Decreasing availability
− Processing of fly ash – new and from ponds
− Increasing imports – variability in lot to lot
− Increased pricing
• Strong demand for other pozzolans driven by strong construction market
− Silica fume – merger of traditional suppliers, rationalization, entrance of new supplier.
Availability decreased, price increases not as much as expected.
− Slag completely sold out.
− Construction industry looking for alternatives – natural pozzolans, metakaolin, rice hull
husks
• Effect on Oilfield Cements? Chemistries, availability and pricing

8. CHALLENGES WITH OTHER ADDITIVES
• Changing Chemistries for admixtures as durability requirements in
construction affected demand.
− Accelerators – switch to nonchloride accelerators
− Plasticizers – changing chemistries for durability making “older” technologies less
available.
• Issues with materials imported from China
− Environmental controls have significantly affected many segments of industry
− Many raw materials suppliers being rationalized.
− Safety concerns affected ports
− Tariffs?
• Changing processes that affected materials that are produced as
byproducts
− Change in papermaking processes decreasing availability of lignocellulose materials.
• Strong Global economies
− Competition by construction industry affecting supply and pricing.

9. Opportunities in Cement
• Can the changing chemistries in cement be of benefit to the industry?
Negatives in construction may be of benefit in oilfield – slower set times,
slower strength gain, poor air entrainment etc.
• New alternative cements. Both ACI and ASTM have launched evaluation
of “new” alternative cements for the construction industry, could these be
of benefit in the oilfield?
− Clinkered cements
• Calcium aluminate
• Reactive belite
• Calcium sulphoaluminates
• Carbonated calcium silicate
− Calcined cements
• Magnesium cements – oxychloride, oxysulfate, phosphate, silicate
− Non-Clinkered cements
• Alkali activated
• Fly ash cements
• Slag cements
• Glass cements

10. Opportunities in Heavy Weight Additives
• Significant work has been done on high density aggregates for use
in concrete for nuclear shielding
• While the materials commonly used in oilfield cements ( barite,
hematite and Ilmenite) are commonly used for this application, a
variety of alternative have proven successful and can provide
alternatives
− Magnetite
− Ferrophosphorous
− Steel punchings, iron shot
− Bauxite
− Goethite
− Boron frit
− Slag

11. Opportunities in Light Weight Additives
• In construction demand for lightweight concrete has increased thus
spurring development of new materials for its use.
• Mineral/processed lightweight aggregates
− Calcined expanded slate
− Volcanic pumice
− Calcined shale
• Manufactured Additives
− Pelletized expanded slag
- Sintered pulverized fly ash aggregate
− Vermiculite
− Perlite
− Polystyrene

12. Opportunities in Accelerators
• Calcium chloride has been used in the industry for years and
continues to be the main material used in oilfield cements
• It’s use has been limited in construction due to corrosivity of the
chloride ions – in fact it is banned by most DOT’s
• A lot of work has been conducted in developing non-chloride
accelerators. This may be of interest in oilfield cement as they can
provide more control and formulated to perform at varying
temperatures
• Most common non-chloride accelerators formulas use in
construction are based on calcium nitrate, calcium formate, sodium
nitrate, thiocyanates (sodium and potassium)

13. Opportunities in Retarders
• Requirements for retardation differ significantly between regular concrete
and oilfield cements as this is significantly affected by temperature
• In spite of the differences, same basic materials are used for both -
lignosulfonates, cellulose derivatives, hydroxycarboxylic acids
• Little work has been done though on inorganics used with concrete for this
function in oilfield cements thus present an opportunity
− Oxides of lead and zinc
− Phosphates
− Magnesium salts
− Fluorates
− Borates
• A relatively new class of admixtures have been developed to stop cement
hydration till it is ready (Extended set admixtures). These are proprietary
fomulations but base on phosphonates, phosphorous containing organic
acids, gluconates.

14. Opportunities in Shrinkage Control
• In general technology for shrinkage reducing (SRA’s) used in standard
concrete not effective in oilwell cements because volatile and thus no
effect at the higher temperatures.
• Standard approach is to use compounds that expand during hydration in a
quantity sufficient to compensate for the cement shrinkage. Issue is
efficacy over a range of temps.
• Common expansion materials used are calcium sulfoaluminate, calcined
calcium oxide, magnesium oxide.
• Use of magnesium oxide as a shrinkage compensating additive has been
increasing because different grades calcined at different temperatures
provide a range of reactivity that can be tailored to well temp.
− CCM Light burn MgO is more reactive thus lower levels needed and effective up to 200 F
− Deadburn most effective at temp. above 200 F
− Manufacturers matter

15. MgO Shrinkage Compensating
Data Courtesy of Riteks Oilfield Solutions

16. Cement Binder Demand Forecast
0
100
200
300
400
500
600
700
2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 2022
NA CEMENT DEMAND K MT FORECAST
LOW HIGH

17. NA Cement Additives Market Forecast
• Oilwell Cement Additive market difficult to define as it comprises a variety
of mineral and nonmineral components.
• Best estimate that can be provided is total cost vs. cost of cement for
cementing operations
• Wide variabilities expected depending on changes in formulations
• Estimate based on US $ M of total market at supplier level
• Estimate Breakdown as follows:
− Heavy Weight Additives 5%
− Light Weight Additives 7.5%
− Accelerators 7.5%
− Retarders 12.5%
− Fluid Loss Additives 22.5%
− Loss Circulation Additives 20%
− Expansion Additives 13%
− Dispersants 10%
− Antifoaming agents 2%

18. NA Cement Additives Market Forecast
0
20
40
60
80
100
120
140
160
180
200
2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 2022
CEMENT ADDITIVE MARKET ESTIMATE US $ M
LOW HIGH

19. NA Cement Additives Market Forecast
US $ M

20. Contact Info
For More Information
Contact
Claudio Manissero
President
ChemCognition LLC
claudio@Chemcognition LLC
+01 - 704-907-5463 (US)