Pentaerythritol encapsulated with boric acid: An efficient composite crosslinker for guar gum fracturing fluid

Commonly used crosslinker agents often have a low crosslinking efficiency with guar gum, the major component of fracturing fluid for crude oil recovery, and it often required a high loading of guar gum for achieving desired recovery from low-permeability reservoir. Nevertheless, a high-loading of guar gum might result in excessive residue and reduce the conductivity of the reservoir. Therefore, boric acid, a commonly used crosslinking agent, was introduced onto the surface of pentaerythritol to afford a composite crosslinking agent denoted as PB. The as-prepared PB crosslinker was characterized by Fourier-transform infrared spectrometry. The guar gum fracturing gel crosslinked with the PB had fantastic viscoelasticity and thermal stability and could reduce the guar gum loading by 16.7%, with boric acid as a control. Besides, the gel-broken liquid had good compatibility with the simulated water and caused reduced damage to rock core, showing potential for hydraulic fracturing of low-permeability reservoirs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48528.     

耐高温胍胶压裂液及其对储层的伤害机理研究进展

随着油气资源的勘探开发不断向深层超深层储层发展,常规胍胶压裂液不能满足高温超高温储层压裂施工需求。国内外学者致力于从胍胶耐温改性与新型耐高温交联剂合成两个方向提升胍胶压裂液的耐温性能,同时研究了胍胶压裂液对储层的伤害机理,取得了较大进展。本文回顾了近年来国内外耐高温胍胶压裂液的发展动态,阐述了关于耐高温改性胍胶和耐高温交联剂合成的研究现状,从胍胶压裂液对储层的伤害类型和伤害机理角度进行了总结,重点分析了胍胶压裂液对高温储层伤害机理的研究进展。最后指出,应该继续通过化学改性进一步提高胍胶自身的耐温性能,同时加强对破胶剂和纳米交联剂的研究,并提出高效低伤害的纳米交联压裂液是耐高温胍胶压裂液未来可能的发展方向。     

Preparation and characterization of nano‐SiO2 reinforced alginate‐based nanocomposite films (II)

Crosslinked alginate‐based nanocomposites at different SiO₂ contents were prepared successfully by blending the nano‐SiO₂ solution into low concentration alginate solution (0.5 wt %), with the alginate concentration increased step by step to the resulted concentration, in this course glycerol was used as plasticizer and 5 wt % CaCl₂ as crosslinker. The combined effect of SiO₂ content (1.5–8 wt %) on the microstructural, physical, mechanical, and optical properties of the nanocomposite films were investigated. The results showed that tensile strength and elongation was improved by about 40.33% and 89%, respectively, upon increasing the SiO₂ content to 4.5 wt %. In addition, water vapor permeability and swelling degree decreased by 19% and 16% with increasing SiO₂ content up to 8 and 4.5 wt %, respectively with respect to pure crosslinked alginate film. Thermogravimetric analysis also revealed that nano‐SiO₂ can improve the thermal stability of sodium alginate films produced by this method. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45286.     

Tremendous reinforcing,pore‐stabilizing and response‐accelerating effect of in situ generated nanosilica in thermoresponsive poly(N‐isopropylacrylamide) cryogels

The tremendous reinforcing and pore‐stabilizing effect of in situ formed nanosilica in a highly porous temperature‐responsive poly(N‐isopropylacrylamide) (PNIPA) matrix is demonstrated. A very weakly crosslinked semi‐liquid hydrogel can be reinforced to the point that it displays a fast, extensive and nearly symmetric temperature‐responsiveness in combination with an acceptable modulus. In soft but solid porous PNIPA, only 0.6 wt% of the nanofiller is sufficient to stabilize the pores against collapse upon de‐swelling, thus enabling ultrafast responsiveness. A spectacular effect is achieved with dried porous PNIPA (matrix is glassy, T_g ≈ 140 °C), which in the case of optimal nanosilica amounts can re‐swell in only 3 min. The key importance of efficient hydrogen bridging between PNIPA and SiO₂ is demonstrated by comparing in situ formed nanosilica with similarly sized commercial Ludox particles, the surface of which is saturated with ammonia (for stabilization). Synthesis parameters like the amount of crosslinker and of nanosilica were varied in a wide range, in order to achieve the fastest possible responsiveness of the hydrogels in combination with a high modulus. The porosity, nanosilica distribution, moduli, temperature‐dependent swelling as well as the swelling kinetics of the gels were determined as functions of contents of crosslinker and nanosilica. © 2017 Society of Chemical Industry     

Polymer electrolyte membranes prepared by EB‐crosslinking of sulfonated poly(ether ether ketone) with 1,4‐butanediol

Crosslinked sulfonated poly(ether ether ketone) (SPEEK) membranes were prepared through the electron beam (EB)‐irradiation crosslinking of SPEEK/1,4‐butanediol under various irradiation conditions and used as a proton exchange membrane (PEM) for fuel cell applications. The crosslinked membranes were characterized by gel fraction, a universal testing machine (UTM), dynamic mechanical analysis (DMA), and small‐angle X‐ray scattering (SAXS). The gel fraction of the crosslinked membranes was used to estimate the degree of crosslinking, and the gel fraction was found to be increased with an increase of the crosslinker content and EB‐absorbed dose. The UTM results indicate that a brittle EB‐crosslinked membrane becomes more flexible with an increase in the crosslinker content. The DMA results show that the EB‐crosslinked membranes have well‐developed ionic aggregation regions and the cluster T_g of membranes decrease with an increase in the 1,4‐butanediol crosslinker content. The SAXS results show that the Bragg and persistence distance of crosslinked membranes increase with an increase in the crosslinker content. The proton conductivities of the EB‐crosslinked membranes were more than 9 × 10^?2 S/cm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41760.     

Preparation of conductive polyaniline/nanosilica particle composites through ultrasonic irradiation

Polyaniline/nano‐SiO₂ particle composites were prepared through ultrasonic irradiation. Polymerization of aniline was conducted under ultrasonic irradiation in the presence of two types of nano‐SiO₂: porous nanosilica and spherical nanosilica. The stability of the colloid dispersion, UV–vis spectra, composition, interaction, conductivity, and other characteristics of the composites were examined. It was found that the aggregation of nano‐SiO₂ could be reduced under ultrasonic irradiation and that nanoparticles were redispersed in the aqueous solution. The formed polyaniline deposited on the surface of the nanoparticle, which led to a core–shell structure. Two particle morphologies, threadlike aggregates with a few spherical nanoparticles for porous nanosilica and spherical particles with a few sandwichlike particles for spherical nanosilica, were observed. X‐ray photoelectron spectroscopy showed that for two types of composites the ratio of Si atoms to N atoms (Si:N) on the surface was much higher than that in the bulk. The UV–vis spectra of the diluted colloid dispersion of polyaniline/nano‐SiO₂ composite particles were similar to those of the polyaniline system. Fourier transform infrared spectroscopy suggested strong interaction between polyaniline and nano‐SiO₂. The conductivity of the polyaniline/porous nanosilica (23.1 wt % polyaniline) and polyaniline/spherical nanosilica (20.6 wt % polyaniline) composites was 2.9 and 0.2 S/cm, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1811–1817, 2003     

Effects of nanosilica on retrogradation properties and structures of thermoplastic cassava starch

Composites of thermoplastic cassava starch (TPS) and nanosilica (SiO₂) were prepared by the melting method. The effect of nano‐SiO₂ on the retrogradation properties and structures of cassava starch was investigated. The retrogradation degree of TPS/nano‐SiO₂ composites increased with increasing retrogradation time. The retrogradation rate of TPS significantly increased after the addition of nano‐SiO₂, but excessive nano‐SiO₂ content leads to a decrease in the retrogradation rate of TPS. According to the Fourier transform infrared spectroscopy results, the retrogradation degree of TPS/nano‐SiO₂ composites increased with the increase of retrogradation time and addition of nano‐SiO₂. Scanning electron microscopy analysis indicated that nano‐SiO₂ particles were uniformly and finely dispersed in the starch materials, but the nano‐SiO₂ particles aggregated in the cassava starch with a further increase in nano‐SiO₂ content. X‐ray diffraction revealed that the crystalline structure of the starch was gradually altered from A‐type to V‐type with the increase of retrogradation time. TPS/SiO₂ composites indicated a mixture of A+V types, and the intensity of the V‐type strengthened with the increase of retrogradation time and SiO₂ content. Polarized light microscopy analysis revealed clear Maltese cross patterns, and the number of spherulites in TPS/nano‐SiO₂ composites increased with increasing retrogradation time and nano‐SiO₂ content, but the retrogradation of starch was inhibited with further increases of nano‐SiO₂ content. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45687.     

有机锆对羧甲基羟丙基瓜胶的交联性能研究

以氧氯化锆和柠檬酸等为原料,合成了适用于羧甲基羟丙基瓜胶在酸性条件下交联的有机锆交联剂,考察了pH值、温度、羧甲基羟丙基瓜胶和交联剂加量等对体系成胶时间的影响,评价了形成冻胶的抗温抗剪切性能、滤失性能和破胶性能.实验发现,在pH值为3.0时,羧甲基羟丙基瓜胶/有机锆体系具有可控的延缓交联特性,质量分数为0.5%和0.6...     

Effects of high nano‐SiO2 contents on properties of epoxy‐modified polybenzoxazine

High‐performance nanosilica composites based on epoxy‐modified polybenzoxazine matrices are developed. Chemorheological study of benzoxazine–epoxy resin mixtures reveals that processing window of the benzoxazine resin (BA‐a) is substantially broadened with an addition of the liquid epoxy. Glass transition temperature (T _g) of the BA‐a copolymerized with epoxy resin shows a synergistic behavior with a maximum T _g value (174°C) at the benzoxazine–epoxy mass ratio of 80:20. The copolymer at this composition is also used as a matrix for nano‐SiO₂ composites. A very low melt viscosity of the benzoxazine–epoxy mixtures promotes good processability with the maximum attainable nano‐SiO₂ loading up to 35 wt%. From scanning electron microscopy investigation, fracture surface of the 35 wt% nano‐SiO₂‐filled benzoxazine–epoxy composite reveals relatively homogeneous distribution of the nano‐SiO₂ in the copolymer with good particle wet‐out. In addition, very high reinforcing effect was also observed in such high content of the nano‐SiO₂, i.e., about 2.5 times in modulus improvement. This improvement is attributed to the strong bonding between the copolymer matrix and the nano‐SiO₂ through ether linkage as confirmed by Fourier‐transform infrared investigation. POLYM. COMPOS., 38:2261–2271, 2017. © 2015 Society of Plastics Engineers     

Synthesis and performance evaluation of crosslinker for seawater-based fracturing fluid

Zirconium is one of the most commonly used crosslinkers for guar gum-based fracturing fluid. Nevertheless, it is difficult for zirconium crosslinkers applied in fracturing to possess both high temperature resistance and adjustable crosslinking time. Meanwhile, few people did systematical research on the crosslinking process of fracturing fluid. In this study, an organic zirconium crosslinker with high temperature resistance and controllable crosslinking time was synthesized. The seawater-based fracturing fluid gel prepared with the crosslinker could perform well under 170°C. Oscillatory shear experiments were conducted to analyze the rheology of the gelation process. Moreover, steady-state shear and micro-rheological tests were conducted to analyze the dynamic and static crosslinking process of the fracturing fluid, respectively. Meanwhile, rheo-kinetic equation was used to fit the data and the effects that various factors had on the gelation process were illustrated thoroughly. This study not only prepared an organic zirconium crosslinker with good performances, but also explored the crosslinking process of fracturing fluid gel, which could improve its further application in oilfields.     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and property investigation of crosslinked alginate/silicon dioxide nanocomposite films

Crosslinked nanocomposite films of sodium alginate (SA) and silicon dioxide (SiO₂) with different SiO₂ loading values were prepared by in situ synthesis. Biocomposite films were produced by solution casting and solvent evaporation with glycerol as the plasticizer and calcium chloride as the crosslinking agent. The effects of the addition of nano silicon dioxide (nano‐SiO₂) in SA on the microstructural, physical, mechanical, and optical properties of the nanocomposite films were characterized. The results show that nano‐SiO₂ was dispersed homogeneously in the SA matrix; it thereby formed a strong interfacial interaction between the nano‐SiO₂ particles and the matrix. The transparency of the bionanocomposite films was enhanced. Thermogravimetric analysis also revealed that nano‐SiO₂ improved the thermal stability of the SA films. The incorporation of SiO₂ further reduced the water vapor permeability and swelling degree and significantly increased the tensile strength and elongation, which are parameters important for packaging industries. Finally, the lower light transmission of UV light from 200 to 250 nm indicated that SA/SiO₂ nanocomposite films could potentially be used to prevent lipid damage by UV light in food conservation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43489.     

Synergistic effects of silica nanoparticles and reactive compatibilizer on the compatibilization of polystyrene/polyamide 6 blends

This study examines the selective dispersion of nano‐SiO₂ in polystyrene (PS) and polyamide 6 (PA6) blends. With the coupling assistance of 3‐methacryloylpropyl trimethoxysilane (MPS), nano‐SiO₂ surfaces are grafted with PS chains of different molecular weights (SiO₂–MPS–PS) or reactive random copolymer of styrene (St) and 3‐isopropenyl‐α,α′‐dimethylbenzene isocyanate (TMI) to produce SiO₂–MPS–P(St–co–TMI). The isocyanate groups of the reactive copolymer can react with the terminal group of the PA6 to form a graft copolymer, which helps in controlling the location of nano‐SiO₂ between the PS and PA6 phases. Field‐emission scanning electron microscopy imaging combined with the rheological method was used to investigate the location and dispersion of nano‐SiO₂, as well as the morphology of the PS/PA6 blends, at low nano‐SiO₂ loading. Compared with pristine SiO₂, the modified SiO₂ with different chain lengths adjusted the PA6 phase with refined size and narrow size distribution because of the strong interaction with both phases. The SiO₂–MPS–PS with appropriate length is the most effective. The use of nano‐SiO₂ along with the reactive compatibilizer provides synergistic effects for improving the compatibilization of PS/PA6 blends. POLYM. ENG. SCI., 57:1301–1310, 2017. © 2017 Society of Plastics Engineers     

The preparation of microcrystalline cellulose–nanoSiO2 hybrid materials and their application in tire tread compounds

Microcrystalline cellulose (MCC) was hybridized with nano‐SiO₂ to improve its interaction with a rubber matrix. The hybrids (MCC–SiO₂) were prepared with the “microreactor” and “sol–gel” technologies, using MCC as the carrier and tetraethoxysilane as the precursor. The structure and morphology of the hybrids were studied by infrared spectrometry, thermogravimetric analysis, and scanning electron microscopy. The results showed that the nano‐SiO₂ had been loaded successfully on the surface of the MCC with a loading ratio of approximately 30%. The nano‐SiO₂ can take on the morphologies of particles, tubes, or rods by controlling the size of the “microreactor”. The hybrids were then used in silica/SSBR compounds to replace part of the silica, and their effects on the physio‐mechanical and dynamic properties were discussed. The results showed that the vulcanizates with the hybrids had improved physio‐mechanical and dynamic properties. The vulcanizates of MCC–SiO₂ also had a higher wet‐skid resistance and a lower rolling resistance than did the silica vulcanizates when they were used in tire tread compounds. The SEM photos showed that the interfacial adhesion between the MCC and rubber was improved. The size of the MCC hybrids was also in situ decreased during the processing of the rubber compounds. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44796.     

Effect of amphoteric dispersant on the dispersion properties of nano‐SiO2 particles

An amphoteric polycarboxylate dispersant (APC) was synthesized by copolymerization of acrylic acid (AA), methacryloxyethyltrimethyl ammonium chloride (DMC), and isopentenol polyoxyethylene ether (IPEG). The molecular structure of APC was characterized by FT‐IR, ¹H‐NMR, and GPC. Effect of the dosage of APC on the rheological performance of nano‐SiO₂ suspension was investigated by measurements of the plastic viscosity. The results indicated that the best dispersion effect of APC was obtained when the dosage of APC was about 10 wt % (by the weight percent of nano‐SiO₂), which can maintain the dispersion of nano‐SiO₂ suspension uniformly for 4 h without settlement. Meanwhile, the zeta potential value on the surface of nano‐SiO₂ particles shows that the better dispersion performance of APC was attributed to the solvation water film formed by the polyoxyethylene side chains and the electrostatic repulsion formed by positively groups (C?N⁺) on the APC structure combined with ‐SiO^– groups on the surface of nano‐SiO₂ particles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45075.     

Noticeable viscosity reduction of polycarbonate melts caused jointly by nano‐silica filling and TLCP fibrillation

Nano‐SiO₂ was introduced into in‐situ composites of polycarbonate (PC) and a thermotropic liquid crystalline polymer (TLCP) using a twin‐screw extruder. The rheology of these composites was characterized with capillary rheometry, and the morphology of the dispersed TLCP observed with scanning electron microscopy. The rheological data revealed that the viscosity decrease of PC melts by only the addition up to 20 wt% TLCP remained smaller than 30%, while it became ～48% upon further addition of only about 1 wt% nano‐SiO₂ and larger than 60% upon ～9 wt% nano‐SiO₂ filling, in contrast to a 50% viscosity increase of PC melts with increase in nanosilica loading up to ～9 wt%. These silica‐filled composites exhibited markedly low viscosity, especially at relatively high shear rates. The morphology of TLCP extracted from unfilled and silica‐filled composites indicated that the largest viscosity reduction was correlated well with the fibrillation of TLCP droplets enhanced by nano‐SiO₂. The TLCP/SiO₂/PC composites exhibited rheological hybrid effect with fillers at nanometer scale. POLYM. ENG. SCI., 47:757–764, 2007. © 2007 Society of Plastics Engineers     

一种酸性压裂液研制及其性能评价

针对低渗透、碱敏性储层,研制了一种以有机锆为交联剂,羧甲基羟丙基胍胶为增稠剂的酸性压裂液体系,并对压裂液相关性能进行了系统评价。实验结果表明,当增稠剂溶液浓度为0.4%,交联比为100∶2,破胶剂加量为0.06%时,与压裂液助剂粘土稳定剂、缓蚀剂、助排剂等配制的压裂液破胶液粘度为1.013 mPa.s,残渣含量为261 mg/L,防膨率为90.5%,表面张力为27.6 mN/m,平均缓蚀速率为0.826 g/(h.m2),在90℃下滤失速率为0.575×10-5 m/min0.5,对储层的伤害率小于15%。     

Fracturing fluid cleanup by controlled release of enzymes from polyelectrolyte complex nanoparticles

Water‐based polymer gels are used widely in the oil and gas industry to viscosify fluids used in the hydraulic fracturing of production wells, where they serve to increase the force applied to the rock and to improve the transport of proppants used to maintain the fracture after formation. After fracturing, the gel must be degraded to a low viscosity with enzymes or gel breakers. Existing systems add the breaker either directly to the gelant or encapsulated in beads that are crushed when the applied pressure is released and the fractures close. In the former case, the gel may be broken prematurely, and this may prevent efficient fracture propagation and proppant transport, whereas in the latter case, the breaker may not be uniformly distributed throughout the gel, with the result that the gel is incompletely broken and the hydraulic conductivity of the well is reduced. To obtain delayed release, combined with the homogeneous distribution of enzyme throughout the gel, polyethylenimine–dextran sulfate polyelectrolyte complexes were used to entrap pectinase. Such particles were originally developed to entrap pharmaceuticals, and we previously demonstrated their ability to delay the release of gel crosslinking agents for oilfield applications. The degradation of both the viscosity and viscoelastic moduli of borate‐crosslinked guar gel by pectinase loaded in polyelectrolyte nanoparticles was delayed by up to 12 h, compared to about 2 h for equivalent systems where the pectinase was not entrapped. The combination of homogeneous mixing and the delayed release of enzymes packaged in polyelectrolyte complex nanoparticles showed promise for improved cleanup after hydraulic fracturing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effects of functionalization on the thermal and tribo‐mechanical behaviors of neat and grafted polyethylene nanocomposites

This article presents research on the influence of a coupling agent γ‐methacryloxypropyltrimethoxysilane (MEMO) and cross‐linking agent dicumyl peroxide (DCP) on thermal and nanomechanical properties of neat and waste polyethylene (WPE) as well as their blend. Modification of nanosilica by silanization was performed under supercritical conditions of carbon dioxide‐ethanol mixture. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), indentation as well as scratch testing at nanoscale were employed for characterization of the polymer matrix with unmodified and modified nano‐SiO₂ particles. Low amounts of the peroxide and silanized nano‐SiO₂ particles in the composite formulation significantly improved thermal and tribo‐mechanical behavior at nanoscale. POLYM. COMPOS., 34:1710–1719, 2013. © 2013 Society of Plastics Engineers     

Surface‐activated nanosilica treated with silane coupling agents/polypropylene composites: Mechanical,morphological, and thermal studies

This work reports the mechanical, morphological, and thermal properties of the polypropylene (PP) nanocomposites containing nanosilica (nano‐SiO₂) which were treated by different functional group silane coupling agents. Four types of silane coupling agents namely aminopropyltriethoxy silane (APTES), glycidyloxypropyltrimethoxy silane (GPTMS), trimethoxysilylpropyl methacrylate (TMPM), and dichlorodimethyl silane (DCMS) were used to modify the surface‐activated nanosilica. To enhance the effectiveness of the coupling, nanosilica was chemically activated and analyzed through FTIR and X‐ray photo electron spectroscopy (XPS). The highest tensile strength was recorded by the activated nanocomposites treated with APTES followed by nanocomposite treated with GPTMS, TMPM, and DCMS, respectively. The addition of silane coupling agents into nano‐SiO₂/PP system further improved the tensile modulus of the PP nanocomposites. From the transmission electron microscopy (TEM) analysis, activated nanosilica treated with APTES showed better nanosilica dispersion in the PP matrix and lesser agglomeration occurred when compared with the other silane coupling agents which were used in this study. Surface activation process does not effectively increase the degree of crystallinity and thermal stability on the PP nanocomposites. However, with the assistance of the surface treatment, it was found that the thermal behavior of the PP nanocomposites had been enhanced. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers