Journal of Polymer Research

, 26:33 | Cite as

A hybrid nanocomposite of poly(styrene-methyl methacrylate- acrylic acid) /clay as a novel rheology-improvement additive for drilling fluids

  • Nima Mohamadian
  • Hamzeh Ghorbani
  • David A. WoodEmail author
  • Maryam Abdollahi Khoshmardan


The hybrid-polymer nanocomposite poly(styrene-methyl methacrylate- acrylic acid) /nanoclay was synthesized by miniemulsion polymerization for novel use as a drilling fluid additive. Three low-solid-drilling fluids (bentonite-based; natural polymer-based; nanoclay-based) were formulated using the hybrid nanocomposite as an additive and their rheological performance compared. The polymer/clay hybrid nanoparticles significantly improve rheological and filtration properties of the drilling fluids and they remain stable at high pressure, high temperature and harsh salinity conditions. The fluids’ filtration properties improve as the concentration of the polymer/nanoclay-hybrid-nanoparticles increases. The clay-based nanocomposite additive had the highest positive impact on the rheological behavior of low-solids polymer-based drilling fluid. Analysis of rheological properties and filtration loss of the drilling fluids suggest that the optimum nanoclay concentration in the hybrid-polymer nanocomposite is about 5 wt.%.

Graphical Abstract


Hybrid-nanocomposite additive Polymer-nanoclay-based drilling fluids Low-solids drilling fluids Rheological properties Filtration-loss control Miniemulsion polymerization 



American Petroleum Institute


Ammonium persulfate, (NH4)2S2O8


Apparent viscosity


Fourier-transform infrared spectroscopy


Gel strength


Polymer clay nanocomposite


Plastic viscosity


Sodium dodecyl sulfate, CH3(CH2)11SO4Na


Xanthan gum


X-Ray powder diffraction


X-Ray fluorescence


Yield point


Supplementary material

10965_2019_1696_MOESM1_ESM.docx (656 kb)
ESM 1 A supplementary file is available to readers that provides additional information including an extended discussion regarding the attributes of PCN as a drilling additive, more detaisls on the measurement of rheological properties and two schematic diagrams representing the PCN structure (DOCX 655 kb)


  1. 1.
    Caenn R, Darley HC, Gray GR (2011) Composition and properties of drilling and completion fluids, Gulf professional publishingGoogle Scholar
  2. 2.
    Vryzas Z, Kelessidis VC (2017) Nano-based drilling fluids: a review. Energies 10(4):540CrossRefGoogle Scholar
  3. 3.
    ASME Shale Shaker Committee (2011) Drilling fluids processing handbook, Elsevier. 700 pages ISBN: 9780750677752Google Scholar
  4. 4.
    AzarJJ, Samuel GR (2007) Drilling engineering, PennWell booksGoogle Scholar
  5. 5.
    Shah SN, Shanker, NH, Ogugbue CC (2010) Future challenges of drilling fluids and their rheological measurements. in AADE fluids conference and exhibition, Houston, TexasGoogle Scholar
  6. 6.
    Amani M, Al-Jubouri M, Shadravan A (2012) Comparative study of using oil-based mud versus water-based mud in HPHT fields. Advances in Petroleum Exploration and Development 4(2):18–27Google Scholar
  7. 7.
    Shakib JT, Kanani V, Pourafshary P (2016) Nano-clays as additives for controlling filtration properties of water–bentonite suspensions. J Pet Sci Eng 138:257–264CrossRefGoogle Scholar
  8. 8.
    Abduo M, Dahab A, Abuseda H, AbdulAziz AM, Elhossieny M (2016) Comparative study of using water-based mud containing multiwall carbon nanotubes versus oil-based mud in HPHT fields. Egypt J Pet 25(4):459–464CrossRefGoogle Scholar
  9. 9.
    Zakaria M, Husein MM, Harlan G (2012) Novel nanoparticle-based drilling fluid with improved characteristics. SPE-156992-MS in SPE international oilfield nanotechnology conference and exhibition 12–14 June. Society of Petroleum Engineers, Noordwijk, The Netherlands. CrossRefGoogle Scholar
  10. 10.
    Husein MM, Zakaria MF, Hareland G (2016) Novel nanoparticle-containing drilling fluids to mitigate fluid loss. Google Patents. Accessed 9 Jan 2019
  11. 11.
    Hoelscher KP, De Stefano G, Riley M, Young S (2012) Application of nanotechnology in drilling fluids. SPE-157031-MS in: SPE international oilfield nanotechnology conference and exhibition, 12–14 June. Society of Petroleum Engineers, Noordwijk, The Netherlands. CrossRefGoogle Scholar
  12. 12.
    Nasser J, Jesil A, Mohiuddin T, Al Ruqeshi M, Devi G, Mohataram S (2013) Experimental investigation of drilling fluid performance as nanoparticles. World Journal of Nano Science and Engineering 3(03):57CrossRefGoogle Scholar
  13. 13.
    William JKM, Ponmani S, Samuel R, Nagarajan R, Sangwai JS (2014) Effect of CuO and ZnO nanofluids in xanthan gum on thermal, electrical and high pressure rheology of water-based drilling fluids. J Pet Sci Eng 117:15–27CrossRefGoogle Scholar
  14. 14.
    Ponmani S, William JKM, Samuel R, Nagarajan R, Sangwai JS (2014) Formation and characterization of thermal and electrical properties of CuO and ZnO nanofluids in xanthan gum. Colloids Surf A Physicochem Eng Asp 443:37–43CrossRefGoogle Scholar
  15. 15.
    Zakaria F, Mostafavi V, Hareland G, Husein M (2011) Design and application of novel Nano Drilling fluids to mitigate circulation loss problems during oil well drilling operations. World Nano Conference and Expo 2011:13–16Google Scholar
  16. 16.
    Borisov AS, Husein M, Hareland G (2015) A field application of nanoparticle-based invert emulsion drilling fluids. J Nanopart Res 17(8):340CrossRefGoogle Scholar
  17. 17.
    Cheraghian G, Hemmati M, Masihi M, Bazgir S (2013) An experimental investigation of the enhanced oil recovery and improved performance of drilling fluids using titanium dioxide and fumed silica nanoparticles. J Nanostruct Chem 3(1):78CrossRefGoogle Scholar
  18. 18.
    Ghanbari S, Kazemzadeh E, Soleymani M, Naderifar A (2016) A facile method for synthesis and dispersion of silica nanoparticles in water-based drilling fluid. Colloid Polym Sci 294(2):381–388CrossRefGoogle Scholar
  19. 19.
    Hassani SS, Amrollahi A, Rashidi A, Soleymani M, Rayatdoost S (2016) The effect of nanoparticles on the heat transfer properties of drilling fluids. J Pet Sci Eng 146:183–190CrossRefGoogle Scholar
  20. 20.
    Mohammadi M, Kouhi M, Sarrafi A, Schaffie M (2015) Studying rheological behavior of nanoclay as oil well drilling fluid. Res Chem Intermed 41(5):2823–2831CrossRefGoogle Scholar
  21. 21.
    Saboori R, Sabbaghi S, Mowla D, Soltani A (2012) Decreasing of water loss and mud cake thickness by CMC nanoparticles in mud drilling. Int J Nano Dimens 3(2):101–104Google Scholar
  22. 22.
    Kang Y, She J, Zhang H, You L, Song M (2016) Strengthening shale wellbore with silica nanoparticles drilling fluid. Petroleum 2(2):189–195CrossRefGoogle Scholar
  23. 23.
    Ismail A, Aftab A, Ibupoto ZH, Zolkifile N (2016) The novel approach for the enhancement of rheological properties of water-based drilling fluids by using multi-walled carbon nanotube, nanosilica and glass beads. J Pet Sci Eng 139:264–275CrossRefGoogle Scholar
  24. 24.
    Fazelabdolabadi B, Khodadadi AA, Sedaghatzadeh M (2015) Thermal and rheological properties improvement of drilling fluids using functionalized carbon nanotubes. Appl Nanosci 5(6):651–659CrossRefGoogle Scholar
  25. 25.
    Kosynkin DV, Ceriotti G, Wilson KC, Lomeda JR, Scorsone JT, Patel AD, Friedheim JE, Tour JM (2011) Graphene oxide as a high-performance fluid-loss-control additive in water-based drilling fluids. ACS Appl Mater Interfaces 4(1):222–227PubMedCrossRefGoogle Scholar
  26. 26.
    Abdou M, Al-Sabagh A, Dardir M (2013) Evaluation of Egyptian bentonite and nano-bentonite as drilling mud. Egypt J Pet 22(1):53–59CrossRefGoogle Scholar
  27. 27.
    Abdo J, Haneef M (2013) Clay nanoparticles modified drilling fluids for drilling of deep hydrocarbon wells. Appl Clay Sci 86:76–82CrossRefGoogle Scholar
  28. 28.
    Cheraghian G, Wu Q, Mostofi M, Li M-C, Afrand M, Sangwai JS (2018) Effect of a novel clay/silica nanocomposite on water-based drilling fluids: improvements in rheological and filtration properties. Colloids Surf A Physicochem Eng Asp 555:339–350CrossRefGoogle Scholar
  29. 29.
    Nizamania AA, Ismail AR, Juninb R, Qadeer A (2017) Synthesis of Titania-bentonite nanocomposite and its applications in water-based drilling fluids. Chem Eng Trans 56:949–954Google Scholar
  30. 30.
    Li M-C, Wu Q, Song K, Qing Y, Wu Y (2015) Cellulose nanoparticles as modifiers for rheology and fluid loss in bentonite water-based fluids. ACS Appl Mater Interfaces 7(8):5006–5016PubMedCrossRefGoogle Scholar
  31. 31.
    Li M-C, Wu Q, Song K, De Hoop CF, Lee S, Qing Y, Wu Y (2015) Cellulose nanocrystals and polyanionic cellulose as additives in bentonite water-based drilling fluids: rheological modeling and filtration mechanisms. Ind Eng Chem Res 55(1):133–143CrossRefGoogle Scholar
  32. 32.
    Riveland FA (2013) Investigation of nanoparticles for enhanced filtration properties of drilling fluid. MSc Thesis. Norwegian University of Science and Technology, Trondheim, pp 68. Accessed 9 Jan 2019
  33. 33.
    Srivatsa JT, Ziaja MB (2011) An experimental investigation on use of nanoparticles as fluid loss additives in a surfactant-polymer based drilling fluids. IPTC-14952-MS in International Petroleum Technology Conference 15–17 November, Bangkok, Thailand. CrossRefGoogle Scholar
  34. 34.
    Sadeghalvaad M, Sabbaghi S (2015) The effect of the TiO2/polyacrylamide nanocomposite on water-based drilling fluid properties. Powder Technol 272:113–119CrossRefGoogle Scholar
  35. 35.
    Mao H, Qiu Z, Shen Z, Huang W (2015) Hydrophobic associated polymer based silica nanoparticles composite with core–shell structure as a filtrate reducer for drilling fluid at utra-high temperature. J Pet Sci Eng 129:1–14CrossRefGoogle Scholar
  36. 36.
    Mao H, Qiu Z, Shen Z, Huang W, Zhong H, Dai W (2015) Novel hydrophobic associated polymer based nano-silica composite with core–shell structure for intelligent drilling fluid under ultra-high temperature and ultra-high pressure. Prog Nat Sci Mater Int 25(1):90–93CrossRefGoogle Scholar
  37. 37.
    Jain R, Mahto V, Sharma V (2015) Evaluation of polyacrylamide-grafted-polyethylene glycol/silica nanocomposite as potential additive in water based drilling mud for reactive shale formation. J Nat Gas Sci Eng 26:526–537CrossRefGoogle Scholar
  38. 38.
    Huo J-h, Z-g P, Ye Z-b, Feng Q, Zheng Y, Zhang J, Liu X (2018) Investigation of synthesized polymer on the rheological and filtration performance of water-based drilling fluid system. J Pet Sci Eng 165:655–663CrossRefGoogle Scholar
  39. 39.
    Jain R, Mahto V (2015) Evaluation of polyacrylamide/clay composite as a potential drilling fluid additive in inhibitive water based drilling fluid system. J Pet Sci Eng 133:612–621CrossRefGoogle Scholar
  40. 40.
    Jain R, Mahto TK, Mahto V (2016) Rheological investigations of water based drilling fluid system developed using synthesized nanocomposite. Korea-Australia Rheol J 28(1):55–65CrossRefGoogle Scholar
  41. 41.
    Jung Y, Son Y-H, Lee J-K, Phuoc TX, Soong Y, Chyu MK (2011) Rheological behavior of clay–nanoparticle hybrid-added bentonite suspensions: specific role of hybrid additives on the gelation of clay-based fluids. ACS Appl Mater Interfaces 3(9):3515–3522PubMedCrossRefGoogle Scholar
  42. 42.
    Barry MM, Jung Y, Lee J-K, Phuoc TX, Chyu MK (2015) Fluid filtration and rheological properties of nanoparticle additive and intercalated clay hybrid bentonite drilling fluids. J Pet Sci Eng 127:338–346CrossRefGoogle Scholar
  43. 43.
    Noah A, El Semary M, Youssef A, El-Safty M (2017) Enhancement of yield point at high pressure high temperature wells by using polymer nanocomposites based on ZnO & CaCO3 nanoparticles. Egypt J Pet 26(1):33–40CrossRefGoogle Scholar
  44. 44.
    Madkour TM, Fadl S, Dardir M, Mekewi MA (2016) High performance nature of biodegradable polymeric nanocomposites for oil-well drilling fluids. Egypt J Pet 25(2):281–291CrossRefGoogle Scholar
  45. 45.
    Sadeghalvaad M, Sabbaghi S (2017) Application of TiO2/polyacrylamide Core–Shell nanocomposite as an additive for controlling rheological and filtration properties of water-based drilling fluid. J Nanofluids 6(2):205–212CrossRefGoogle Scholar
  46. 46.
    Knopp D, Tang D, Niessner R (2009) Bioanalytical applications of biomolecule-functionalized nanometer-sized doped silica particles. Anal Chim Acta 647(1):14–30PubMedCrossRefGoogle Scholar
  47. 47.
    Tang P, Sudol ED, Adams M, Silebi C, El Aasser M (1992) Miniemulsion polymerization. ACS Symp Ser:72–98Google Scholar
  48. 48.
    Asua JM (2002) Miniemulsion polymerization. Prog Polym Sci 27(7):1283–1346CrossRefGoogle Scholar
  49. 49.
    Schork FJ, Luo Y, Smulders W, Russum JP, Butté A, Fontenot K (2005) Miniemulsion polymerization. Polym Part:129–255Google Scholar
  50. 50.
    Chern C (2006) Emulsion polymerization mechanisms and kinetics. Prog Polym Sci 31(5):443–486CrossRefGoogle Scholar
  51. 51.
    Rahme R, Graillat C, Farzi G, McKenna TF, Hamaide T (2010) Miniemulsion polymerizations using static mixers: towards high biocompatible hydrophobe contents. Macromol Chem Phys 211(21):2331–2338CrossRefGoogle Scholar
  52. 52.
    Farzi G, Mortezaei M, Badiei A (2011) Relationship between droplet size and fluid flow characteristics in miniemulsion polymerization of methyl methacrylate. J Appl Polym Sci 120(3):1591–1596CrossRefGoogle Scholar
  53. 53.
    Farzi G, Mortezaei M (2015) Acrylic latexes prepared via Miniemulsion polymerization technique for improvement of soil behavior. J Nanosci Technol:50–54Google Scholar
  54. 54.
    Allahvirdizadeh P, Kuru E, Parlaktuna M (2016) Experimental investigation of solids transport in horizontal concentric annuli using water and drag reducing polymer-based fluids. J Nat Gas Sci Eng 35:1070–1078CrossRefGoogle Scholar
  55. 55.
    Boul PJ, Reddy B, Zhang J, Thaemlitz C (2017) Functionalized nanosilicas as shale inhibitors in water-based drilling fluids. SPE Drill Complet 32(02):121–130CrossRefGoogle Scholar
  56. 56.
    Farzi G, Bourgeat-Lami E, McKenna TF (2009) Miniemulsions using static mixers: a feasibility study using simple in-line static mixers. J Appl Polym Sci 114(6):3875–3881CrossRefGoogle Scholar
  57. 57.
    Nazarabady MM, Farzi GA (2016) Morphology control of silica/poly (methyl methacrylate-co-styrene) hybrid nanoparticles via multiple-miniemulsion approach. E-Polymers 16(2):91–98CrossRefGoogle Scholar
  58. 58.
    Koo JH (2016) Fundamentals, properties, and applications of polymer nanocomposites. Cambridge University pressGoogle Scholar
  59. 59.
    Xu M, Choi YS, Kim YK, Wang KH, Chung IJ (2003) Synthesis and characterization of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites via emulsion polymerization with AMPS. Polymer 44(2003):6387–6395CrossRefGoogle Scholar
  60. 60.
    Prasad K, Nikzad M, Sbarski I (2018) Permeability control in polymeric systems: a review. J Polym Res 25(232).
  61. 61.
    Sodeifian G, Nikooamal HR, Yousefi AA (2012) Molecular dynamics study of epoxy/clay nanocomposites: rheology and molecular confinement. J Polym Res 19(9897).
  62. 62.
    Ray SS, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 28:1539–1641CrossRefGoogle Scholar
  63. 63.
    Mahto V, Sharma V (2004) Rheological study of a water based oil well drilling fluid. J Pet Sci Eng 45(1–2):123–128CrossRefGoogle Scholar
  64. 64.
    Exploration Department API (2017) Recommended practice standard procedure for field testing water-based drilling fluids, American Petroleum Institute. API RP 13B-2, Field Testing Oil-Based Drilling Fluids.
  65. 65.
    Yang L, Jiang G, Shi Y, Lin X, Yang X (2017) Application of ionic liquid to a high-performance calcium-resistant additive for filtration control of bentonite/water-based drilling fluids. J Mater Sci 52(11):6362–6375CrossRefGoogle Scholar
  66. 66.
    Ahmad HM, Kamal MS, Al-Harthi MA (2018) Rheological and filtration properties of clay-polymer systems: impact of polymer structure. Appl Clay Sci 160:226–237CrossRefGoogle Scholar
  67. 67.
    Ahmad HM, Kamal MS, Al-Harthi MA (2018) High molecular weight copolymers as rheology modifier and fluid loss additive for water-based drilling fluids. J Mol Liq 252:133–143CrossRefGoogle Scholar
  68. 68.
    Khezri K, Haddadi-Asl V, Roghani-Mamaqani H, Salami-Kalaiahi M (2012) Synthesis of clay-dispersed poly(styrene-co-methyl methacrylate) nanocomposite via miniemulsion atom transfer radical polymerization: a reverse approach. J Appl Polym Sci 124(3):2278–2286CrossRefGoogle Scholar
  69. 69.
    Kamal MS, Sultan AS, Al-Mubaiyedh UA, Hussein IA (2015) Review on polymer flooding: rheology, adsorption, stability, and field applications of various polymer systems. Polym Rev 55(3):491–530CrossRefGoogle Scholar
  70. 70.
    Volpert E, Selb J, Candau F (1998) Associating behaviour of polyacrylamides hydrophobically modified with dihexylacrylamide. Polymer 39(5):1025–1033CrossRefGoogle Scholar
  71. 71.
    Heller H, Keren R (2003) Anionic polyacrylamide polymer adsorption by pyrophyllite and montmorillonite. Clay Clay Miner 51(3):334–339CrossRefGoogle Scholar
  72. 72.
    Gunawan AY, Sukarno P, Soewono E (2011) Modeling of mud filtrate invasion and damage zone formation. J Pet Sci Eng 77(3–4):359–364Google Scholar
  73. 73.
    Audibert A, Argillier J (1995) Thermal stability of sulfonated polymers. SPE-28953-MS In: SPE International Symposium on Oilfield Chemistry, 4–17 February. Society of Petroleum Engineers, San Antonio, Texas, U.SA. CrossRefGoogle Scholar
  74. 74.
    Jia H, Chen H, Guo S (2017) Fluid loss control mechanism of using polymer gel pill based on multi-crosslinking during overbalanced well workover and completion. Fuel 210:207–216CrossRefGoogle Scholar
  75. 75.
    Liyi C, Sheng W, Changwen Y (2014) Effect of gas hydrate drilling fluids using low solid phase mud system in plateau permafrost. Procedia Eng 2014(73):318–325CrossRefGoogle Scholar
  76. 76.
    Hughes B (2006) Drilling fluids reference manual. Houston, TexasGoogle Scholar
  77. 77.
    Lal M (1999) Shale stability: drilling fluid interaction and shale strength. SPE-54356-MS in SPE Asia Pacific Oil and Gas Conference and Exhibition, 20–22 April. Indonesia Society of Petroleum Engineers, Jakarta. CrossRefGoogle Scholar
  78. 78.
    Massoud A, Waly S (2014) Preparation and characterization of poly (acrylic acid-dimethylaminoethylmethacrylate) as amphoteric exchange resin and its adsorption properties. Colloid Polym Sci 292(12):3077–3083CrossRefGoogle Scholar
  79. 79.
    Jonsson B, Labbez C, Cabane B (2008) Interaction of nanometric clay platelets. Langmuir 24(20):11406–11413PubMedCrossRefGoogle Scholar
  80. 80.
    Xie B, Ting L, Zhang Y, Liu C (2018) Rheological properties of bentonite-free water-based drilling fluids with novel polymer viscosifier. J Pet Sci Eng 164:302–310CrossRefGoogle Scholar
  81. 81.
    Yan L, Wang C, Xu B, Sun J, Yue W, Yang Z (2013) Preparation of a novel amphiphilic comb-like terpolymer as viscosifying additive in low-solid drilling fluid. Mater Lett 105:232–235CrossRefGoogle Scholar
  82. 82.
    Mohammadi M, Ghorbani H, Wood D, Hormozi HK (2018) Rheological and filtration characteristics of drilling fluids enhanced by nanoparticles with selected additives: an experimental study. Advs Geo-Energy Res 2(3):228–236CrossRefGoogle Scholar
  83. 83.
    Hamed SB, Belhadri M (2009) Rheological properties of biopolymers drilling fluids. J Pet Sci Eng 67(3–4):84–90CrossRefGoogle Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.Young Researchers and Elite Club, Omidiyeh BranchIslamic Azad UniversityOmidiyehIran
  2. 2.Young Researchers and Elite Club, Ahvaz BranchIslamic Azad UniversityAhvazIran
  3. 3.DWA Energy LimitedLincolnUK
  4. 4.Department of Chemical and Petroleum EngineeringSharif University of TechnologyTehranIran

Personalised recommendations