نشریه پژوهش های کاربردی مهندسی شیمی - پلیمر
سال پنجم شماره 3 (پیاپی 17، پاییز 1400)

Research subject: Prediction of the wellbore temperature during the downhole operations and its effects on the stress condition of the tubulars is one of the important factors in design of the completion, production and stimulation operations in oil and gas wells. Temperature changes during the life of the well can change the stress condition of the pipes inside the well, such as the tubing and the casing, and cause problems such as wellhead displacement or buckling of the tubulars, which is dangerous in both terms of safety of the well and personnel and it can also be economically inefficient. Research approach: In this study, various operations during the life of a well such as running the completion string, production start-up, the well shut in, acid injection and other common operations in oil wells were simulated in a practical order. Temperature changes during these operations and their effect on the stress condition of the wellbore casing and tubing were investigated. Main results The results showed that long-term production of the well causes the most temperature changes in the well. This increase in the temperature reached a maximum value at a depth of 430 ft, which is the mud line depth.  Further, because the pipe is fixed, it buckles and creates torque at deeper well depths. The results also showed that the time required for the temperature to be completely stable is about a few months, and this should be taken into account in the tubing pressure test analysis.

Biodegradable compounds with high mechanical and thermal properties are one of the intersting research topics. Polylactic acid is an aliphatic polyester with high biodegradability and flexibility. It, however, suffers from several weaknesses such as high permeability to water vapor and gases, low glass transition temperature, poor thermal stability and brittleness which can be improved by the incorporation of nano-scale fillers giving rise to bionanocomposites. The aim of this study was to investigate the effect of the simultaneous incorporation of cellulose nanocrystals and nanosilver on the mechanical, thermal and water vapor permeability behavior of polylactic acid-based films.

Polylactic acid films and their bionanocomposites containing different levels of cellulose nanocrystals (0.01, 0.03 and 0.05 g) and nanosilver (0.01 g) were prepared by solution casting method. To improve compatibility and miscibility of the polymer, cellulose nanocrystals were reacted with acetic anhydride and modified. FTIR spectroscopy, tensile test, thermal properties (DSC), migration test and antibacterial properties were used to study the properties of the samples. The water vapor permeability of the samples were also measured.

The addition of cellulose nanocrystals, increased the glass transition temperature (Tg) and melting point (Tm) of the samples. The presence of cellulose nanocrystals increased the tensile strength and modulus of elasticity of the bionanocomposite relative to pure polylactic acid. With the addition of cellulose nanocrystals, permeability was reduced by about 25%. As the amount of cellulose nanocrystals increased, the swelling and water absorption of the samples increased significantly. The migration rate of the samples also decreased after the addition of nanocellulose.

Hydrodesulfurization is one of the effective methods to remove sulfur compounds from oil fractions and improve fuel quality. One of the major challenges in this process is to find the proper catalyst support that performs best. In the meantime, modified supports with zeolite have allocated a lot of attention due to their strong acidic sites, specific surface area and high hydrothermal and chemical stability; But the acidity and volume of zeolite mesopores need to be corrected.

In this study, first, hierarchical Y zeolite was prepared using post-synthesis (Dealumination) and using ammonium form of zeolite and NH4F solution (0.75 M) at 90˚C for 3h under reflux conditions. Physicochemical properties of zeolite were investigated by BET, FESEM, FTIR, AAS and XRD analyzes. Modified zeolites were used in the support synthesis of the HDS process catalyst. The sulfidation and performance evaluation of the prepared catalysts were carried out in the fixed-bed microreactor were performed with diesel cutting feed from the Isomax unit of the target refinery.

The results show that the volume of mesopores, specific surface area and SiO2/Al2O3 ratio in hierarchical zeolites has increased 0.073 cm3 g-1, 783.36 m2 g-1 and 5.2, respectively (initial values are 0.032 cm3 g-1, 567.18 m2 g-1 and 4.5). The results of zeolite analysis show the preservation of the structure and crystallinity during the zeolite modification process. The effect of zeolite modification, especially the Si/Al ratio variations, mesopores and specific surface area, was investigated on the activity of NiMo/Zeolite+Al2O3 catalysts. Increasing the acidity and improving the physicochemical properties of the modified zeolites has increased the catalyst performance in the process of diesel hydrodesulfurization (Conversion= 90%). Improving the activity of catalysts can be attributed to the positive effect of zeolites on the dispersion of the metallic site, surface area, acidity, optimal size of pores and volume of catalyst mesopores.

Solar cells has gained a great attention as a green, renewable and cheap energy resources. To overcome the challenging technical problems and improve their competitiveness with silicone solar cells, the design, synthesis and development of new materials with engineered band gap energies has found an undeniable importance.

Herein, the synthesis of a polymer with donor-acceptor structure based on polyaniline grafted to ZnO nanoparticles at one end and naphthalene moiety at the other end of chains, and investigation of their chemical structure, composition, morphology, optical and electrochemical properties is reported. The chemical structure of the materials were analyzed by FT-IR and 1H NMR spectroscopy. The organic and inorganic contents of materials were determined by thermal gravimetric analysis (TGA) and atomic absorption spectroscopy (AAS) techniques. The morphology and size of nanoparticles were observed by scanning electron microscopy (SEM). The optical and electrical band gap energy of the samples were measured by ultraviolet visible-diffuse reflectance (UV-Vis-DRS) spectroscopy and cyclic voltammetry (CV) diagrams.

The chemical structure of designed materials has been successfully confirmed by the results of FT-IR and 1H NMR spectra. TGA and AAS analysis have indicated that the synthesized final material has contained about 10% of ZnO and 90% of organic parts including toluene-2,4-diisocyanate, 2,4-diaminotoluene, polyaniline and naphthalene groups. An almost highly uniform spherical nanoparticles with sizes about 70 nm has been observed by SEM images. UV-Vis-DRS spectroscopy and CV diagrams have revealed that by grafting ZnO nanoparticles and naphthalene moiety to the polyaniline chain ends, the optical and electrical band gap energy of the sample were lowered to 1.19 and 0.95 eV, respectively. It was concluded that the grafted groups to chain ends has increased the length of conjugated system, lowering the energy level of lowest unoccupied molecular orbital (LUMO) and increasing the energy level of highest occupied molecular orbital (HOMO). Detailed analysis of CV diagrams has indicated that the effect in lowering of LUMO has been a bit more pronounced than the increasing of HOMO energy level.

The use of hydroxyapatite nanoparticles (HAp) in traditional polymers as reinforcing agent has been reported. While there are a limited number of reports regarding the effect of HAp morphology on the mechanical properties of the polymeric matrix, no research on this effect on supermolecular polymers has been reported so far. This study investigates the hypothesis that incorporation of unidirectionally grown HAp nanoparticles (rod-like nanoparticles, rHAp) into supramolecular polycaprolactone (SPCL) leads to the synthesis of a new bioactive construct.

For this, rHAp nanoparticles were first synthesized by microemulsion method and then functionalized with 2-ureido-4[1H]-pyrimidinone (UPy) groups. Moreover, PCL was functionalized and converted to supramolecular structures by reacting the hydroxyl terminal groups with UPy groups. Finally, SPCL/rHAp nanocomposites were synthesized by solution casting method and their structure and properties were examined using attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM), universal testing machine and simulated body fluid (SBF).

According to the results, microemulsion is an efficient procedure for the synthesis of rod-like nanoparticles with high phase purity. On the other hand, based on the results, it is possible to functionalize these nanoparticles with UPy. Tensile test showed that by incorporation of these modified nanoparticles into SPCL, a significant increase in both elastic modulus and tensile strength can be observed. In fact, while the initial PCL was a waxy solid, modification with UPy and then incorporation of modified nanoparticles made it an elastic material. Finally, the obtained results indicated high bioactivity of supramolecular nanocomposites compared to the sample without filler. Therefore, supramolecular SPCL/rHAp nanocomposites with bioactive properties and dynamic character can be used as a suitable replacement for bone tissue defects.

Activated carbon is a porous absorbent with reasonable specific surface area, pore volume, and pore size distribution for many applications such as adsorption. This material is obtained from various natural sources of carbon. Due to increasing demand for activated carbon, the economical precursors have been highly noticed. In the meanwhile, black liquor, industrial residue from Lignin Kraft process in paper factories, has high amount of carbon which can be used as an appropriate and cheap precursor for activated carbon production, and make high value added.

In this study, at first, lignin was extracted from black liquor, prepared from Iran wood & paper industries-Chouka factory, under defined conditions and investigation of pH effect, and then, powdered carbon was synthesized from extracted lignin using chemical activation method by phosphoric acid chemical agent. To consider the effects of activation temperature parameter on activated carbon structure, including specific surface area, pore volume, and pore size distribution, three activation temperature of 400, 500 and 600 ⁰C in impregnation ratio of 2 were investigated. To study the physical and morphological properties of sensitized absorbents, they were analyzed by BET, SEM, and FTIR methods.

The results confirmed that the highest amount of lignin with a similar structure to the degraded lignin was recovered at pH = 2. Investigation of the effect of activation temperature parameter suggested that the activation temperature of 500 °C can be a reasonable temperature for the synthesis of high specific surface area activated carbon and increasing the temperature above 500 °C is not effective. Among these sensitized adsorbents, the activated carbon sensitized in activation temperature of 500 ⁰C showed the highest specific surface area and the pore volume of 1573.31 m2/g and 0.89 cm3/g respectively, which exhibits the high potential of this precursor as activated carbon adsorbent.

In this research, epoxy modification was successfully performed by polyurethane and its effect on abrasion and adhesion properties have been investigated. The most important concern in the blending of these polymers was the formation of gels upon exposure of epoxy resin and isocyanate in polyurethane.

One solution to overcome this problem is to control the chemical activity of Isocyanate. Therefore to reduce the chemical activity of isocyanate and prevent gel formation due to the combination of epoxy and polyurethane, first polyurethane prepolymer containing 3.58 wt.% NCO was prepared by mixing poly tetra methylene glycol 2000 (PTMG 2000) and toluene di isocyanate (2,4-TDI); and then by adding 20 wt.% of it to the epoxy resin, the curing process was completed by using dimethyl thio-toluene di amine (DMTDA) as a common curing agent and also specific heat treatment.

Fourier transformation infrared spectroscopy results showed that the modification process has been successful by elimination of the peaks related to epoxide and isocyanate groups in the prepared sample in addition to the formation of a broad peak related to secondary hydroxyl group (C-O) due to the opening of epoxide rings. Pull off tests also confirmed increasing adhesion to carbon steel substrate as a result of secondary hydroxyl generation through this blending. Although, the Persoz hardness of modified epoxy decreased by 5%, but with a 17-fold reduction of elastic modulus (as per tensile test result), abrasion resistance improved 6 times according to abrasion test. Finally, joining of the cavities to each other is introduced as the abrasion mechanism by considering the field emission- scanning electron microscope images.

In this study, EDTA-functionalized Fe3O4@SiO2 magnetic nanocomposites with core-shell structure were synthesized to remove divalent cadmium ions from aqueous solutions.

During the first step, Fe3O4@SiO2 nanosphere core-shell is synthesized using nano Fe3O4 as the core, TEOS as the silica source and PVA as the surfactant. This strategy relies on the covalently bonding of ethylendiaminetetraacetic acid to bis(3-aminopropyl)amine and cyanuric chloride functionalized magnetic nanoparticles. In the next step, characteristics of surface functional groups, crystal structure, magnetic properties, size and surface morphology of these nanoparticles were investigated, identified and analyzed using physico-chemical characterization techniques including fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), dynamic light scattering (DLS), vibration sample magnetometry (VSM) and Brunauer-Emmett-Teller (BET) surface area analyzer.  The adsorbent, due to its magnetic property, could be simply separated from the reaction mixture by a permanent magnet and reused in five consecutive cycles without considerable loss in its activity.

To probe the nature of the adsorbent, various experiments were investigated like adsorbent dose and contact time were optimized. Kinetic studies and the effect of different amounts of adsorbent to remove divalent cadmium ions from aqueous solutions show a maximum adsorption of 94% at ambient temperature. Moreover, the recyclability of Fe3O4@SiO2-EDTA was investigated in order to remove the divalent cation for successive adsorption-desorption cycles. All the results of studies show that the synthetic nanocomposite Fe3O4@SiO2-EDTA is an effective, recyclable adsorbent with excellent performance for the removal of divalent cadmium.