A review of nuclear magnetic resonance(NMR) technology applied in the characterization of polymer gels for petroleum reservoir conformance control

Polymer gel systems have been widely applied to control excessive water and improve oil recovery(IOR)in petroleum reservoirs.They are usually divided into two main types,in-situ cross-linked polymer gels,and pre-formed polymer gels.In recent years,nuclear magnetic resonance(NMR) technology has been gradually applied to the research of polymer gel systems due to its unique analysis advantages.This paper is intent to review these works systematically.For in-situ cross-linked polymer gel systems,NMR can be used to characterize the chemical structure changes of the polymer,the cross-linker,and the auxiliary agent in the formulation of the polymer gel systems.Moreover,the gelation time and the gel strength of the in-situ cross-linked polymer gel systems can also be measured by NMR.For pre-formed polymer gels,NMR can be employed to detect the chemical structure of the designed products.Last,the NMR method can evaluate the plugging,water control,and oil improvement performance of the polymer gels in porous media without using dopants.This review can help readers build a more systematic understanding of the application of NMR technology in polymer gel systems for IOR and help re searchers to more deeply study the performance of polymer gel systems.

A HYBRID POLYMER GEL AND ITS STATIC NONERGODICITY

We used a thermally reversible hybrid gel made of billions of physically jam-packed swollen thermally sensitivepoly(N-isopropyl-acrylamide) chemical microgels. Laser light scattering study on a series of such hybrid gels formed atdifferent gelling rates and temperatures revealed that the position-dependence of the scattering speckle pattern(staticnonergodicity) came from large voids formed during the sol-gel transition. With a proper preparation, such a nonergodicitycould be completely removed, indicating that the static nonergodicity generally observed in a gel is not indinsic, but comesfrom the clustering "island" structure formed during the gelation process.

Fabrication of a highly efficient new nanocomposite polymer gel for controlling the excess water production in petroleum reservoirs and increasing the performance of enhanced oil recovery processes

A new nanocomposite polymer gel is synthesized for reduction of excess water production in petroleum reservoirs at real operating conditions.This new nanocomposite gel contains SiO2 nanoparticles,partially hydrolyzed polyacrylamide(HPAM)and chromium triacetate.High pressure and high temperature tests using porous carbonate core are carried out to evaluate the effects of nanoparticles on the synthesized polymer gel performance.It is shown that the residual resistance factor ratio of water to oil using the synthesized polymer gel nanocomposite in this work is much higher than that of the ordinary polymer gels.The presented results confirm the high performance of the synthesized nanocomposite polymer gel for decreasing the water flow through porous carbonate bed.A mathematical model for description of oil and water flow behavior in the presence of synthesized nanocomposite polymer gel is also presented.The presented nano polymer gel leads to considerable cost saving in enhanced oil recovery(EOR)processes.

Study of the reinforced mechanism of fly ash on amphiphilic polymer gel

Amphiphilic polymer gels are widely used in heterogeneous reservoirs for conformance control technology.However,in high temperature and high salinity of calcium and magnesium reservoirs,amphiphilic polymer gels cannot maintain effective performance.In this work,a novel reinforced amphiphilic polymer gel(F-PADC gel)was prepared by physically mixing polymer solution and fly ash(FA),which is an extremely low cost material.The viscoelasticity and stability of the F-PADC gel were studied by rheometry and micro-rheometry.The reinforced mechanism of FA on amphiphilic polymer gels was revealed.The results show that the addition of FA can make the gel more robust with a denser network structure.On the fifth day,the elastic modulus(G’)increases from 5.2 to 7.0 Pa and the viscosity modulus(G")increases from 0.4 to 0.6 Pa at the frequency of 1 Hz,which improves the viscoelasticity of the gel system.More importantly,the F-PADC gel does not degrade after aging at 85℃for 180 d.And its viscoelasticity increases obviously,G′and G"increase to 110.0 Pa and 3.5 Pa,respectively,showing excellent anti-aging stability.Moreover,FA amphiphilic polymer gels have a good injectivity and a perfect plugging rate of 98.86%,which is better than that of sole amphiphilic polymer gels.This novel mixed FA amphiphilic polymer gels can prove to be a better alternative to conventional polymer gels to enhance oil recovery in high temperature and high salinity reservoirs.

SURFACE DYNAMIC FRICTION OF POLYMER GELS

The sliding friction of various kinds of hydrogels has been studied and it was found that the frictional behaviors ofthe hydrogels do not conform to Amonton's law F=μW which well describes the friction of solids. The frictional force andits dependence on the load are quite different depending on the chemical structures of the gels, surface properties of theopposing substrates, and the measurement condition. The gel friction is explained in terms of interracial interaction, eitherattractive or repulsive, between the polymer chain and the solid surface. According to this model, the friction is ascribed tothe viscous flow of solvent at the interface in the repulsive case. In the attractive case, the force to detach the adsorbing chainfrom the substrate appears as friction. The surface adhesion between glass particles and gels measured by AFM showed agood correlation with the friction, which supported the repulsion-adsorption model proposed by the authors.

Bacterial Cellulose/Zwitterionic Dual-network Porous Gel Polymer Electrolytes with High Ionic Conductivity

Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.

Bifunctional TiO_(2-x)nanofibers enhanced gel polymer electrolyte for high performance lithium metal batteries

Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.

Research Progress of Polymer Fire Extinguishing Gel and Its Application in Forest Fire Prevention

The paper summarizes the structure and water-absorbing mechanism,classification,and preparation method of polymer fire extinguishing gel,and prospects for its application in aerial firefighting,forest ground fire extinguishing,opening of firebreaks,and mitigating human casualties in forest fire extinguishing.

The ternary combination of polymer gel, microsphere and surfactant for conformance control and oil displacement to improve oil recovery in strong heterogeneous reservoir

The reservoir heterogeneity of Suizhong 36-1 oilfield is very obvious,the average permeability reaches 2000mD.Long-term water injection development leads to serious water channeling in high permeability layers,resulting in ineffective circulation of injected water and reduction of oil recovery.It is urgent to form an effective EOR method.In this paper,the oil displacement effect of different combination slugs including polymer gel,polymer microsphere and surfactant is evaluated by means of conformance control and chemical flooding.Three-layer heterogeneous 3-D plate model is used for oil displacement experiment.The experimental results show that the combination slug sequentially composed of polymer gel,polymer microspheres and surfactant have the best oil displacement effect with the oil recovery increment by 21.2% after the first water flooding.In addition,using the best slug combination for two rounds flooding,the recovery factor increased by 28.2% compared with the first water flooding.This paper provides some new insights for enhanced oil recovery in strong heterogeneity reservoir.

Effects of nanoparticles, polymer and accelerator concentrations, and salinity on gelation behavior of polymer gel systems for water shut-off jobs in oil reservoirs

Excess water production is one of the crucial complications in the oil industry,leading to a rapid decline in oil production.To overcome this problem,different polymer gels are used to block the water's path to reduce water production.In the present work,polymer gel systems were prepared with polymers namely partially hydrolyzed polyacrylamide(PHPA),organic crosslinkers like hexamine,and hydroquinone with the incorporation of silica and alumina nanoparticles.Nanoparticles are used to enhance the stability of the gel framework in high salinity and high temperature reservoir environment.When designing the polymer gel system,factors such as pH,thermal stability,brine composition,injection rate,and chemical concentration were considered.Concentrations of PHPA and nanoparticles were varied from 1 to 2 wt% and 0.25e1.0 wt% respectively for the preparation of different gel systems.The concentration of the organic crosslinker was extended from 5000 to 11000 ppm for investigating the effect on gelation time.Brine concentration was chosen from 2 to 8 wt% to find the impact of high salinity.Succinic acid as an accelerator was also used to study the effect on gelation time,and it was found that the gelation time is reduced as the concentration of succinic acid increases.The prepared polymer solution was taken in a test tube and was kept inside a hot air oven at 95℃ to perceive the gelation time and nature of the produced gel.Results showed that nanoparticles do not influence the gelation time,but they considerably affect gel stability.However,concentrations of polymer,accelerator,and salt(salinity)have significant effects on the gelation behavior of the gel systems.

A novel profile modification HPF-Co gel satisfied with fractured low permeability reservoirs in high temperature and high salinity

Conformance control and water plugging are a widely used EOR method in mature oilfields.However,majority of conformance control and water plugging agents are unavoidable dehydrated situation in high-temperature and high-salinity low permeability reservoirs.Consequently,a novel conformance control system HPF-Co gel,based on high-temperature stabilizer(CoCl_(2)·H_(2)O,CCH)is developed.The HPF-Co bulk gel has better performances with high temperature(120℃)and high salinity(1×10^(5)mg/L).According to Sydansk coding system,the gel strength of HPF-Co with CCH is increased to code G.The dehydration rate of HPF-Co gel is 32.0%after aging for 150 d at 120℃,showing excellent thermal stability.The rheological properties of HPF gel and HPF-Co gel are also studied.The results show that the storage modulus(G′)of HPF-Co gel is always greater than that of HPF gel.The effect of CCH on the microstructure of the gel is studied.The results show that the HPF-Co gel with CCH has a denser gel network,and the diameter of the three-dimensional network skeleton is 1.5-3.5μm.After 90 d of aging,HPF-Co gel still has a good three-dimensional structure.Infrared spectroscopy results show that CCH forms coordination bonds with N and O atoms in the gel amide group,which can suppress the vibration of cross-linked sites and improve the stability at high temperature.Fractured core plugging test determines the optimized polymer gel injection strategy and injection velocity with HPF-Co bulk gel system,plugging rate exceeding 98%.Moreover,the results of subsequent waterflooding recovery can be improved by 17%.

A gel polymer electrolyte with IL@UiO-66-NH_(2) as fillers for high-performance all-solid-state lithium metal batteries

All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance caused by the poor Li~+transport kinetics due to the solid-solid contacts between the electrodes and the solid-state electrolytes.Herein,a novel gel polymer electrolyte(UPP-5)composed of ionic liquid incorporated metal-organic frameworks nanoparticles(IL@MOFs)is designed,it exhibits satisfying electrochemical performances,consisting of an excellent electrochemical stability window(5.5 V)and an improved Li^(+)transference number of 0.52.Moreover,the Li/UPP-5/LiFePO_(4) full cells present an ultra-stable cycling performance at 0.2C for over 100 cycles almost without any decay in capacities.This study might provide new insight to create an effective Li^(+)conductive network for the development of all-solid-state lithium-ion batteries.

A UV cross-linked gel polymer electrolyte enabling high-rate and high voltage window for quasi-solid-state supercapacitors

Serving as a promising alternative to liquid electrolyte in the application of portable and wearable devices,gel polymer electrolytes(GPEs)are expected to obtain more preferable properties rather than just be satisfied with the merits of high safety and deformability.Here,an easy-operated method is employed to fabricate cross-linked composite polymer membranes used for GPEs assisted by UV irradiation,in which N-doped carbon quantum dots(N-CQDs)and TiO2are introduced as photocatalysts and additives to improve the performances of GPEs.Specifically,N-CQDs participate as a cross-linker to construct the inner porous structure,and TiO2nanoparticles serve as a stabilizer to improve the electrochemical stability of GPEs under high voltage(3.5 V).The excellent thermal and mechanical stability of the membrane fabricated in this work guarantee the safety of the supercapacitors(SCs).This GPE based SC not only exhibits prominent rate performance(105%capacitance retention at the current density of 40A g^(-1))and cyclic stability(85%at 1 A g^(-1)under 3.5 V after 20,000 cycles),but also displays remarkable energy density(42.88 Wh kg^(-1))with high power density(19.3 k W kg^(-1)).Moreover,the superior rate and cycling performances of the as-prepared GPE based flexible SCs under flat and bending state confirm the feasibility of its application in flexible energy storage devices.

Progress in Gel Polymer Electrolytes for Sodium-Ion Batteries

Sodium-ion battery is a potential application system for large-scale energy storage due to the advantage of higher nature abundance and lower production cost of sodium-based materials.However,there exist inevitably the safety problems such as flammability due to the use of the same type of organic liquid electrolyte with lithium-ion battery.Gel polymer electrolytes are being considered as an effective solution to replace conventional organic liquid electrolytes for building safer sodium-ion batteries.In this review paper,the authors present a comprehensive overview of the research progress in electrochemical and physical properties of the gel polymer electrolyte-based sodium batteries.The gel polymer electrolytes based on different polymer hosts namely poly(ethylene oxide),poly(acrylonitrile),poly(methyl methacrylate),poly(vinylidene fluoride),poly(vinylidene fluoride-hexafluoro propylene),and other new polymer networks are summarized.The ionic conductivity,ion transference number,electrochemical window,thermal stability,mechanical property,and interfacial issue with electrodes of gel polymer electrolytes,and the corresponding influence factors are described in detail.Furthermore,the ion transport pathway and ion conduction mechanism are analyzed and discussed.In addition,the advanced gel polymer electrolyte systems including flame-retardant polymer electrolytes,composite gel polymer electrolytes,copolymerization,single-ion conducting polymer electrolytes,etc.with more superior and functional performance are classified and summarized.Finally,the application prospects,development opportunities,remaining challenges,and possible solutions are discussed.

A Fluorescent Supramolecular Crosslinked Polymer Gel Formed by Crown Ether Based Host-Guest Interactions and Aggregation Induced Emission

Based on the combination of B21C7/dialkylammonium salt host-guest interactions and tetraphenylethylene （TPE）-based aggregation-induced emission （AIE） effect, a fluorescent supramolecular crosslinked polymer gel was successfully prepared. Compared with the solution of TPE-containing small molecules, this gel exhibited remarkable fluorescence enhancement due to the AIE effect of TPE units. The ＂gelation induced fluorescence emission＂ phenomenon can be explained by the hindered intramolecular rotation of phenyl rings of TPE. Because of the reversibility and stimuli-responsiveness of the B21C7/dialkylammonium salt host-guest interactions, the transition between the fluorescent supramolecular crosslinked polymer gel and the disassembled sol with very weak fluorescence can be realized by adding pH and thermal stimuli. This novel material contributes to the development of supramolecular chemistry, polymer science and fluorescent materials and offers a new method to construct functional supramolecular materials.

Novel Amphiphilic Polymer Gel Electrolytes Based on PEG-b-GMA-co-MMA

1 Results Gel polymer electrolytes for lithium battery have been widely investigated recently because of their high ion conductivity at room temperature. We synthesized and characterized novel gel electrolytes based on amphiphilic copolymethacrylates containing different lengths of ethylene oxide (EO) chain as ionophilic units and methyl methacrylate (MMA) chain as ionophobic units[1]. Their electrochemical properties were also measured.1H NMR and FTIR analysis results elucidated that PEG-b-glycidyl met...

Synthesis of Copillar[5]arene by Co-oligomerization of Different Monomers and Its Application to Supramolecular Polymer Gel

A copillar[5]arene derivative with different repeating units was synthesized by co-oligomerization of different alkyl ethers.Copillar[5]arene-based supramolecular polymer gel was formed by a self-inclusion complexing in acetonitrile.The supramolecular polymer gel was driven by the C-H•πinteractions,and presented two phases as time went on,and finally,constructed the supramolecular organic framework.Notably,the supramolecular polymer gel showed reversible gel-sol phase transitions upon heating and cooling.Meanwhile,the transparent films formed by the supramloecular gel show the potential application in the field of anti-acid rain materials.

Effect of nano TiO_(2) and SiO_(2) on gelation performance of HPAM/PEI gels for high-temperature reservoir conformance improvement

Nanoparticles have been widely used in polymer gel systems in recent years to improve gelation performance under high-temperature reservoir conditions. However, different types of nanoparticles have different effects on their gelation performance, which has been little researched. In this study, the high-temperature gelation performance, chemical structure, and microstructure of polymer gels prepared from two nanomaterials (i.e., nano-SiO_(2) and nano-TiO_(2)) were measured. The conventional HPAM/PEI polymer gel system was employed as the control sample. Results showed that the addition of nano-TiO_(2) could significantly enhance the gel strength of HPAM/PEI gel at 80 ℃. The gel strength of the enhanced HPAM/PEI gel with 0.1 wt% nano-TiO_(2) could reach grade I. The system also had excellent high-temperature stability at 150 ℃. The enhanced HPAM/PEI gel with 0.02 wt% nano-TiO_(2) reached the maximum gel strength at 150 ℃ with a storage modulus (G′) of 15 Pa, which can meet the need for efficient plugging. However, the nano-SiO_(2) enhanced HPAM/PEI polymer gel system showed weaker gel strength than that with nano-TiO_(2) at both 80 and 150 ℃ with G′ lower than 5 Pa. Microstructures showed that the nano-TiO_(2) enhanced HPAM/PEI gel had denser three-dimensional (3D) mesh structures, which makes the nano-TiO_(2) enhanced HPAM/PEI gel more firmly bound to water. The FT-IR results also confirmed that the chemical structure of the nano-TiO_(2) enhanced HPAM/PEI gel was more thermally stable than nano-SiO_(2) since there was a large amount of –OH groups on the structure surface. Therefore, nano-TiO_(2) was more suitable as the reinforcing material for HPAM/PEI gels for high-temperature petroleum reservoir conformance improvement.

Comprehensive evaluation of chemical breakers for multistage network ultra-high strength gel

Polymer gels have been accepted as a useful tool to address many sealing operations such as drilling and completion,well stimulation,wellbore integrity,water and gas shutoff,etc.Previously,we developed an ultra-high strength gel(USGel)for medium to ultra-low temperature reservoirs.However,the removal of USGel is a difficult problem for most temporary plugging operations.This paper first provides new insights into the mechanism of USGel,where multistage network structure and physical entanglement are the main reasons for USGel possessing ultra-high strength.Then the effects of acid breakers,encapsulated breakers,and oxidation breakers(including H_(2)O_(2),Na_(2)S_(2)O_(8),Ca(ClO)_(2),H_(2)O_(2)+NaOH,Na_(2)S_(2)O_(8)+NaOH,and Ca(ClO)_(2)+NaOH)were evaluated.The effects of component concentration and temperature on the breaking solution were studied,and the corrosion performance,physical simulation and formation damage tests of the breaking solution were carried out.The final formulation of 2%-4%NaOH+4.5%-6%H_(2)O_(2) breaking solution was determined,which can make USGel completely turn into water at 35e105C.The combinations of“acid t breaking solution”,“acid+encapsulated breaker”and“encapsulated breaker+breaking solution”were evaluated for breaking effect.The acid gradually reduced the volume of USGel,which increased the contact area between breaking solution and USGel,and the effect of“4%acid+breaking solution”was 23 times higher than that of breaking solution alone at 35C.However,the acid significantly reduced the strength of USGel.This paper provides new insights into the breaking of high-strength gels with complex network structures.

High-performance PVDF-HFP based gel polymer electrolyte with a safe solvent in Li metal polymer battery

Poly(vinylidenefluoride-co-hexafluoropropylene)(PVDF-HFP)based gel polymer electrolytes are widely studied owing to their electrochemical stability and high dielectric constant.However,most gel polymer electrolytes show unsatisfied safety and interface compatibility due to excessive absorption of volatile and flammable liquid solvents.Herein,by using a safe solvent(N-methyl-2-pyrrolidone)with higher boiling(203℃)and flash points(95℃),we initiatively fabricate a flexible PVDF-HFP based gel polymer electrolyte.The obtained gel polymer electrolyte demonstrates a high ionic conductivity of 7.24×10^−4 S cm−1,an electrochemical window of 5.2 V,and a high lithium transference number of 0.57.As a result,the synthesized polymer electrolyte exhibits a capacity retention of 70%after 500 cycles at 0.5 C,and a discharge capacity of 86 mAh g−1 even at a high current rate of 10 C for LiFePO4 based Li metal batteries.Moreover,a stable Li plating/stripping for more than 500 h is achieved under 0.1 mAh at both room temperature and 70℃.Our results indicate that the PVDF-HFP polymer electrolyte is promising for manufacturing safe and high-performance Li metal polymer batteries.