Free Radical Solution Polymerization Research Articles

Effects and Mechanism of Hyperbranched Phosphate Polycarboxylate Superplasticizers on Reducing Viscosity of Cement Paste.

The adsorption behavior and dispersing capability of hyperbranched phosphated polycarboxylate superplasticizers (PCEs) containing phosphate monoester and phosphate diester were investigated. The hyperbranched structures were constructed using a special monomer dimethylaminoethyl methacrylate (DMAMEA) to create the branches during the polymerization. Meanwhile, the polymer architectures were tailored by varying the content of phosphate monoester and phosphate diester in the backbone via free radical solution polymerization. In contrast to comb-like PCE, hyperbranched PCEs presented a weaker dispersion capability at w/c = 0.29, but with a lower water-to-cement ratio (w/c), the hyperbranched PCEs exhibited a better dispersion capability than the comb-like PCEs. The dynamic light scattering (DLS) and transmission electron microscope (TEM) analysis showed that the adsorption layer of hyperbranched PCEs were thicker than that of comb-like PCEs. A thicker adsorption layer thickness generated thinner diffusion water layer thickness. The increase of the free water amount due to the thinner water diffusion layer is the key mechanism for improving the dispersibility and decreasing the viscosity of cement paste.

Comparative Analysis of Hydrogel Adsorption/Desorption with and without Surfactants.

In this particular study, a hydrogel known as SAP-1 was synthesized through the grafting of acrylic acid-co-acrylamide onto pullulan, resulting in the creation of Pul-g-Poly (acrylic acid-co-acrylamide). Additionally, a sponge hydrogel named SAP-2 was prepared by incorporating the surfactant sodium dodecyl benzene sulfonate (SDBS) into the hydrogel through free radical solution polymerization. To gain further insight into the composition and properties of the hydrogels, various techniques, such as Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance (1H NMR), atomic absorption spectroscopy, and field emission scanning electron microscopy (FE-SEM), were employed. Conversely, the absorption kinetics and the equilibrium capacities of the prepared hydrogels were investigated and analyzed. The outcomes of the investigation indicated that each of the synthesized hydrogels exhibited considerable efficacy as adsorbents for cadmium (II), copper (II), and nickel (II) ions. In particular, SAP-2 gel displayed a remarkable cadmium (II) ion absorption ability, with a rate of 190.72 mg/g. Following closely, SAP-1 gel demonstrated the ability to absorb cadmium (II) ions at a rate of 146.9 mg/g and copper (II) ions at a rate of 154 mg/g. Notably, SAP-2 hydrogel demonstrated the ability to repeat the adsorption-desorption cycles three times for cadmium (II) ions, resulting in absorption capacities of 190.72 mg/g, 100.43 mg/g, and 19.64 mg/g for the first, second, and third cycles, respectively. Thus, based on the abovementioned results, it can be concluded that all the synthesized hydrogels possess promising potential as suitable candidates for the adsorption and desorption of cadmium (II), copper (II), and nickel (II) ions.

Facile Synthesis of Poly(methyl methacrylate) Silica Nanocomposite Monolith by In Situ Free Radical Polymerization of Methyl Methacrylate in the Presence of Functionalized Silica Nanoparticles.

Novel porous poly(methyl methacrylate) (PMMA) silica nanocomposites have been produced by utilization of polymerization-induced phase separation in a simple one-pot approach. A facile free radical polymerization of MMA in the presence of surface methacrylate-functionalized silica nanoparticles was carried out in ethanol-based solvents, successfully producing novel, morphologically designable porous nanocomposite monoliths. Differing from standard free radical polymerization in solution, a mixture of good and poor solvents (ethanol/N,N-dimethylformamide ratio) for the resulting polymer was used to trigger spinodal phase separation. The influence of monomer concentration, as well as solvent composition, on the morphology of the resulting porous polymers has been investigated. Porous monolith structures composed of connected particles and co-continuous morphologies were observed under a scanning electron microscope depending on the polymerization conditions. The resulting polymers were insoluble and showed swelling characteristics in some organic solvents that are capable of dissolving regular PMMA, indicating covalent bonds between the functionalized silica nanoparticles and the polymer chains. The presence of silica particles in the final polymer was proven via an ATR-IR analysis. The glass transition temperature of the present PMMA-silica nanocomposite was higher than that of the conventional PMMA. The porous polymer immersed in a mixed organic solvent showed coloration induced by the Christiansen effect.

Poly(acrylamide)-co-poly(hydroxyethyl)methacrylate-co-poly(cyclohexyl methacrylate) hydrogel platform for stability, storage and biocatalytic applications of urease

In our present work, an explicit crosslinked thermo-responsive hydrogel platform has been developed, by using polyacrylamide (PAAm), poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(cyclohexyl methacrylate) (PCHMA), and then coupled with urease to yield bioconjugates (BCs). Synergic effect of these polymer units provides thermoresponsive nature, optimum crosslinking with desired swelling behaviour, and stability and improved catalytic to Urease in the resultant BCs. Synthesis of the terpolymer has been achieved by employing HEMA (monomer as well as crosslinker), instead of using the conventional crosslinkers, through free radical solution polymerization technique. Various grades of TRPUBs have been fabricated by varying HEMA and CHMA contents while keeping fixed amounts of AAm. Further, the structural analysis of BCs has been done by fourier transform infra-red spectroscopic study and their thermal stabilities have been studied by thermogravimetric analysis. Urea present in TRPUBs has beenanalysed for its hydrolysis atdifferent temperatures viz., 25 °C, 45 °C and 70 °C. Further, the effect of crosslinking, temperature and reaction time on catalytic activities of TRPUBs has been studied. TRPUBs grades have showna maximum swelling capacity up to 5200 %; excellent catalytic activity even at 70 °C; and 85 % activity retention after 18 days storage in buffer medium.

Effects of Structurally Different Tertiary Amines on the Properties of Quaternized Anionic Exchange Membranes Potentially Applicable for Water Electrolysis.

In this work, two structurally different monoamines (trimethylamine [TMA] and N-methylpiperidine [N-MPip]) are used for the amination of a g-VBC-15 graft copolymer, obtained by the functionalization of a mechanically robust, commercially available styrene-butadiene block copolymer (SB) with vinylbenzyl chloride (VBC) via solution free-radical polymerization. Results demonstrate that g-VBC-15-based membranes quaternized with TMA have superior electrochemical performance than N-MPip counterparts; while, the mechanical properties are good and only slightly inferior to those of N-MPip. Therefore, TMA is the selected monoamine to be alternatively mixed with two polyamines (tetramethyl-1,3-propanediamine [TMPDA] and N,N,N',N'',N''-pentamethyldiethylenetriamine [PMDETA]) into different proportions, in order to modulate the average functionality of the amination mixture in terms of number of amine functional groups available for the quaternization reaction of the membranes. g-VBC-15-based membranes derived therefrom are extensively characterized to assess their thermal, mechanical, and ex situ electrochemical properties. Results indicate that membranes quaternized with a TMA/PMDETA mixture (90:10 in mole) display the highest conductivity among all the investigated membranes aminated with polyamine-based mixtures. Moreover, they have comparable mechanical and electrochemical properties to those quaternized with TMA, while exhibiting a reduced water uptake.

High‐temperature resistant copolymer oil well cement retarder: Synthesis, assessment of performance, and mechanism of retardation

AbstractThis work used aqueous solution free radical polymerization to create polymers of 2‐acrylamide‐2‐methylpropane sulfonic acid, itaconic acid, and allyl polyoxyethylene ether as a high‐temperature resistant retarder (APMS/IA/APEG, from now on referred to as AIA). Gel permeation chromatography, fourier transform infrared (FTIR), proton nuclear magnetic resonance (1HNMR), and thermo‐gravimetric analysis (TG) were used to characterize their molecular structure and characteristics. Tests were conducted on the thickening time, rheological characteristics, and compressive strength of AIA in cement slurries. The cement slurry thickened for 276 min at 180°C during the test, and the cement stone's 24‐h compressive strength was consistently more than 20 MPa. The hydration products were analyzed using x‐ray diffractometer and scanning electron microscopy methods, which were then coupled with molecular dynamics simulations to elucidate the AIA retarding mechanism. When AIA is added to a cement slurry, it forms a chelate structure with Ca2+ and a strong adsorption layer on the surfaces of the cement particles. This stops the cement from hydrating. The AIA side chain, APEG, can wrap the active group in AIA at low temperatures. AIA exposes more adsorption groups because of the APEG chains stretching at higher temperatures. AIA can, therefore, be used for deep well operations at high temperatures.

Efficacious adsorption of divalent nickel ions over sodium alginate-g-poly(acrylamide)/hydrolyzed Luffa cylindrica-CoFe2O4 bionanocomposite hydrogel

Existing Ni2+ heavy metal ions in an aqueous medium are highly hazardous for living organisms and humans. Therefore, designing low-cost adsorbents with enhanced effectiveness is essential for removing nickel ions to safeguard public health. In this study, a novel green nanocomposite hydrogel was synthesized through the free radical solution and bulk polymerization method, and its capability to remove divalent nickel ions from aqueous media was examined. The bionanocomposite hydrogel named as SA-g-poly(AAm)/HL-CoFe2O4 was produced by grafting polyacrylamide (AAm) onto sodium alginate (SA) in the presence of a magnetic composite recognized as HL-CoFe2O4, where HL represents hydrolyzed Luffa Cylindrica. By employing FT-IR, XRD, VSM, SEM, EDX-Map, BET, DLS, HPLC, and TGA techniques, morphological evaluation and characterization of the adsorbents were carried out. The performance of the adsorption process was studied under varying operational conditions including pH, temperature, contact duration, initial concentration of pollutant ions, and adsorbent dosage. HPLC analysis proved the non-toxic structure of the bionanocomposite hydrogel. The number of unreacted acrylamide monomers within the hydrogel matrix was measured at 20.82 mg/kg. The optimum conditions was discovered to be pH = 6, room temperature, adsorbent dosage of 1 of g.L−1, initial Ni2+ concentration of 10 mg.L−1, and contact time of 100 min, and the maximum adsorption efficiency at optimal state was calculated as 70.09, 90.25, and 93.83 % for SA-g-poly (AAm), SA-g-poly(AAm)/HL, and SA-g-poly(AAm)/HL-CoFe2O4 samples, respectively. Langmuir isotherm model was in good agreement with the experimental data and the maximum adsorption capacity of SA-g-poly(AAm), SA-g-poly(AAm)/HL, and SA-g-poly(AAm)/HL-CoFe2O4 samples was calculated to be 31.37, 43.15, and 45.19 mg.g−1, respectively. The adsorption process, according to kinetic studies, follows a pseudo-second-order kinetic model. Investigations on thermodynamics also demonstrated that the process is exothermic and spontaneous. Exploring the interference effect of co-existing ions showed that the adsorption efficiency has decreased with concentration enhancement of Ca2+ and Na+ cations in aqueous medium. Furthermore, the adsorption/desorption assessments revealed that after 8 consecutive cycles, there had been no noticeable decline in the adsorption effectiveness. Finally, actual wastewater treatment outcomes demonstrated that the bionanocomposite hydrogel successfully removes heavy metal pollutants from shipbuilding industry effluent. Therefore, the findings revealed that the newly fabricated bionanocomposite hydrogel is an efficient, cost-effective, easy-separable, and green adsorbent that could be potentially utilized to remove divalent nickel ions from wastewater.

Evaluation of newly copolymers and their montmorillonite nanocomposite as cold flow improver for petroleum lubricating oil

The great demand on the energy makes the attention toward modifying lubricating oil. This work tends to prepare the following copolymers; octadecylmethacrylate-co-dodecene (CP1) and octadecylmethacrylate-co-hexadecene (CP2) by free radical solution polymerization using laboratory prepared octadecylmethacrylate monomer with either 1-dodecene or 1-hexadecene. The same monomers also used to prepare their polymers nanocomposite (NP1, NP2) with 1% of nanomontmorolonite by emulsion polymerization. The structures of the prepared polymers and their nanocomposite were elucidated by FTIR, 1HNMR, TGA, DSC, TEM and DLS. These polymers were used as pour point depressant, flow improver and viscosity modifier and showed high efficiency. After comparison of the data of the polymers and their nanocomposite, the nanocomposite give the best results where the pour point decreased from 0 °C to − 18, − 27, − 24 and − 33 °C for CP1, CP2, NP1 and NP2 respectively at the optimum concentration 10,000 ppm. On the other hand the viscosity index increased from 86.57 to 93.25, 92.41, 94.17 and 93.103 for CP1, CP2, NP1 and NP2 respectively, the apparent viscosity increased from 55.863 to 69.31, 119.41, 111.28, and 166.89 cP also the yield stress increased from 652.19 to 1076.3, 1074 and 1480 D/cm2 for CP1, CP2, NP1 and NP2 respectively.

Study on the Effect of Main Chain Molecular Structure on Adsorption, Dispersion, and Hydration of Polycarboxylate Superplasticizers.

Polycarboxylate ether (PCE) with different main chain structures was prepared by aqueous solution free radical polymerization using unsaturated acids containing sulfonic acid groups, acrylamide groups, and carboxyl groups and isoprenyl polyoxyethylene ether (IPEG). The molecular structure was characterized by infrared spectroscopy and gel chromatography, while adsorption, dispersion, and hydration properties were studied using a total organic carbon analyzer, rheometer, and isothermal microcalorimeter, respectively. The results show that the adsorption process of PCE on cement particles is spontaneous physical adsorption. The adsorption forces are mainly electrostatic interaction, and hydrogen bonding. The introduction of sulfonic acid groups and polycarboxylic acid groups reduces the initial adsorption amount of PCE but can accelerate the adsorption rate of PCE on cement and increase the adsorption amount at the adsorption equilibrium. The introduction of acrylamide groups in the PCE main chain is beneficial to the initial dispersion of PCE and can reduce the plastic viscosity of cement slurry. PCE can delay the hydration of cement. The introduction of acrylamide groups and dicarboxylic acid groups in the PCE main chain helps prolong the induction period of cement hydration, while the introduction of sulfonic acid groups is not conducive to its retarding effect.

INVESTIGATION OF PHYSICOCHEMICAL AND THERMAL PROPERTIES OF CLAY-HYDROGEL COMPOSITES

Hydrogels are cross-linked polymeric networks which retain large amounts of water. The hydrogels with response capability to various stimuli such as pH and temperature have received great attention in many fields. In this study, hydrogels were synthesized by free radical solution polymerization through optimization of acrylamide/sodium acrylate mole ratio and ethylene glycol dimethacrylate content. With the addition of sepiolite as filler into the hydrogel network which had highest swelling percent, hydrogel composites were obtained. In the presence of 10 wt% sepiolite, maximum swelling percent was determined as approximately 10600%. Swelling properties of the hydrogel composite including 10 wt% sepiolite was investigated depending on pH, salt effect and temperature. With increasing pH value, swelling percent of the hydrogel composite showed an increase. At high temperatures, the hydrogel composite exhibited higher swelling percent. Swelling tests in 0.1 M NaCl, CaCl2 and FeCl3 solutions revealed that the lowest swelling percent was observed in 0.1 M FeCl3 solution. Fourier transform infrared spectroscopy (FTIR) analyses verified successfully preparation of the hydrogel composites. Regular layers of the sepiolite in the hydrogel network which made water diffusion easily were shown by scanning electron microscopy (SEM) analyses. Thermogravimetric analyses (TGA) indicated that thermal stability of the hydrogel network was increased with the addition of sepiolite.

Synthesis of thermoresponsive PNIPAm nanogel adsorbent by microwave-assisted polymerization for wastewater treatment application

This research demonstrated the fast synthesis technique using microwave-assisted polymerization for the preparation of thermoresponsive poly(N-isopropylacrylamide) (PNIPAm) nanogel which was to be used for paraquat pesticide adsorption. PNIPAm nanogel was synthesized by free-radical polymerization in an aqueous solution using water-soluble ammonium peroxodisulfate (APS) and N,Ń-methylenebisacrylamide (BIS) as initiators and cross-linker, respectively. Microwave irradiation was used as an alternative heating technique and its efficiency was compared to that of the conventional heating method. The results showed that reaction time could be greatly shortened from several hours to only 20 min with the yield of PNIPAm nanogel of approximately 65 % using microwave heating method. The FTIR analysis confirmed that microwave irradiation did not alter the chemical structure of PNIPAm nanogel. The cross-linker concentrations and the sequence of cross-linker addition affected the hydrodynamic diameter of PNIPAm nanogel. The hydrodynamic diameter of swollen PNIPAm nanogels at 25 °C decreased as increasing the cross-linker concentrations and then further decreased when the cross-linker was added after 10 min of the irradiation time. Besides, all PNIPAm nanogel showed well thermoresponsive reversibility over 5 cycles, across the volume phase transition temperature (VPTT) at around 32 °C. The adsorption and release mechanisms of the paraquat took advantage of the phase transition change (swelling-collapse) in response to temperature stimuli, respectively. The PNIPAm nanogel synthesized from the microwave heating method had a profound effect on paraquat adsorption, having 60 – 70 % adsorption with a paraquat release of around 35 – 45 %. These results demonstrated that PNIPAm nanogels could be used as an alternative adsorbent material for industrial wastewater treatment.

N-PMI modified PAZ nanocomposite coatings with self-healing function for anticorrosion and antifouling applications

With the rapid development of the modern industrial marine economy, metal corrosion and biological fouling of marine ships and engineering equipment have become the main problems affecting the development of the marine industry. Traditional single-function coatings have only anti-corrosion or anti-fouling properties, which cannot meet the current needs of marine industry development for coating protection. In this study, a self-healing coating with good anticorrosion and antifouling properties has been prepared upon functionalization of a film forming resin and modification of a nanofiller. Initially, a modified acrylic resin (PAZ/N-PMI) was successfully synthesized by inserting zinc ions and a structural functional monomer (N-phenyl maleimide; N-PMI) into the polymer chain of an acrylic resin using free radical solution polymerization. A fluorinated silica coated hydroxylated multi-walled carbon nanotubes nanocomposite (F-MWCNTs-OH@SiO2) was dispersed in PAZ/N-PMI resin to prepare the composite coating samples. The composite coating showed good performance, in which the antibacterial rate of the composite coating against Staphylococcus aureus and Escherichia coli was >99.98 %. When F-MWCNTs-OH@SiO2 was 3 wt%, the Zf=0.01Hz of the composite coating reached the highest value, which was 3 orders of magnitude higher than that of the PAZ/N-PMI coating. At the same time, the prepared composite coating also exhibited good self-healing properties. This study provides a broad application prospect for the development of high quality marine anti-corrosion and anti-fouling organic coatings.

Comparative Study between a Copolymer Based on Oleic Acid and Its Nanohybrid for Improving the Cold Flow Properties of Diesel Fuel.

The as-synthesized copolymer based on the prepared monomers and its nanohybrid were used for improving the cold flow of diesel fuel that has a vital role in meeting energy needs. The copolymer (AE) was created using the prepared monomers, by free radical solution polymerization of the prepared hexadecylmaleamide and octyloleate ester, and the polymer nanohybrid (NH) was created by emulsion polymerization of the same monomers with 1% nano-SiO2. The chemical structures of the copolymer and its nanohybrid were proved by Fourier transform infrared spectroscopy (FTIR), 1H NMR, dynamic light scattering (DLS), and transmission electron microscopy (TEM). Through exploring the effect of the nanohybrid, before and after adding the dosage of the additives to the diesel fuel, the pour point temperature (PPT), rheological characteristics, and viscosity index were measured. The data were the best for the nanohybrid; the PPT decreased from -3 to -36 °C upon adding 10,000 ppm nanohybrid but decreased from -3 to -30 °C for 10,000 ppm copolymer. In addition, the efficiency of the additives was proved by viscosity-shear rate and shear rate-shear stress curves to give the apparent viscosity, which decreased from 124 cP for the blank to 15.74 and 12.8 cP for AE and NH, respectively; also, the yield stress decreased from 576 D/Cm2 for the blank to 541.44 and 477.9 D/Cm2 for AE and NH, respectively, at room temperature. The viscosity index increased from 116 for the blank to 119 and 121 for the copolymer and the nanohybrid, respectively. Polarizing optical microscopy was performed to show more tiny and separated wax upon adding the additives. The findings showed that delayed crystal precipitation and altered crystal shape with the NH and AE greatly reduced low-temperature viscosity and enhanced the cold flow characteristics of the diesel fuel.

Preparation and performance of durable waterproof adhesive layer for steel bridge deck based on self-stratification effect

In view of the shortcomings of the existing steel bridge deck waterproof adhesive layer (WAL), such as poor durability, high construction cost and long construction period, a new preparation method of waterproof coating with self-stratification effect is proposed. In this paper, poly butyl acrylate-methyl methacrylate–styrene block copolymer with lower glass transition temperature was synthesized by free radical solution polymerization, and 5 kinds of self-stratification coatings were obtained by mixing it with epoxy resin at different mass ratios. The glass transition temperature, thermal stability and chemical composition of acrylic resin were characterized by DSC, TGA, and FT-IR. The self-stratification behavior of the coatings was confirmed by FT-IR, SEM, and water contact angle test. The basic performance and road performance of above self-stratifying waterproof coatings were tested according to specific standards. The results show that these coatings exhibit excellent heat resistance, low temperature flexibility and mechanical properties, namely, average tensile strength can reach 6 MPa, the elongation at break can reach 108 %. Furthermore, the coatings also present extraordinary pull-out strength of 9.51 MPa and excellent water impermeability. Moreover, the tensile strength and elongation at break of the self-stratifying waterproof coatings after UV aging test decreased by 7.3 % and 5.2 %, respectively, indicating that above coating have excellent durability. Therefore, the performance of the coating prepared in this paper fully meets the requirements of the road and bridge waterproof coating standards. The optimum mixing ratio of acrylic resin and epoxy resin is recommended as 3:7 based on their performance. Finally, self-stratifying mechanism of coatings was proposed based on the surface energy theory, which provides theoretical support for the design and preparation of the steel bridge deck WAL.

Poly(N-vinylpyrrolidone)-Laponite XLG Nanocomposite Hydrogels: Characterization, Properties and Comparison with Divinyl Monomer-Crosslinked Hydrogels.

The present work investigates, for the first time, the synthesis and properties of some nanocomposite (NC) hydrogels obtained by the aqueous solution free radical polymerization of N-vinylpyrrolidone (NVP) in the presence of Laponite XLG (XLG) as a crosslinker, in comparison with the corresponding hydrogels prepared by using two conventional crosslinking divinyl monomers: N,N′-methylenebisacrylamide (MBA) and tri(ethylene glycol) divinyl ether (DVE). The structure and properties of the hydrogels were studied by FTIR, TEM, XRD, SEM, swelling and rheological and compressive mechanical measurements. The results showed that DVE and XLG are much better crosslinking agents for the synthesis of PNVP hydrogels than MBA, leading to larger gel fractions and more homogeneous network hydrogels. The hydrogels crosslinked by either DVE or XLG displayed comparable viscoelastic and compressive mechanical properties under the experimental conditions employed. The properties of the XLG-crosslinked hydrogels steadily improved as the clay content increased. The addition of XLG as a second crosslinker together with a divinyl monomer strongly enhanced the material properties in comparison with the hydrogels crosslinked by only one of the crosslinkers involved. The FTIR analyses suggested that the crosslinking of the NC hydrogels was the result of two different interactions occurring between the clay platelets and the PNVP chains. Laponite XLG displayed a uniform distribution within the NC hydrogels, the clay being mostly exfoliated. However, a small number of platelet agglomerations were still present. The PNVP hydrogels described here may find applications for water purification and in the biomedical field as drug delivery systems or wound dressings.

Poly(N-isopropyl acrylamide-co-nbutyl methacrylate)의 분자구조, 진동, 스펙트럼 조사 및 양자화학 DFT 계산

A new copolymer poly(N-isopropylacrylamide-co-nbutylmethacrylate) was synthesized by free radical solution polymerization process using 2,2′-Azobis(2-methylpropionitrile) as an initiator in 1,4-dioxane at 70 °C. The structure of the copolymer was characterized by Fourier Transform Infrared Spectrometer (FTIR), the proton nuclear magnetic resonance (1H NMR), and the ultraviolet-visible spectroscopy (UV-vis) method. Theoretically, density functional theory (DFT) (B3LYP) was utilized to identify the molecular geometry and then examine the vibrational frequencies and electrical characteristics of this molecule, with the 6-31G basis set in the ground state. In dichloromethane solution, UV-vis spectra of the molecule were calculated using the Time-Dependent DFT method. 1H NMR chemical shifts have been calculated with GIAO approximation, and the calculated results show good agreement with experimental chemical shifts.

Preparation, characterization, and evaluation of suspension stabilizer for low‐density cement slurry for cementing

AbstractA low‐density cement slurry system is commonly used in low‐pressure and leakage‐prone cementing. However, the suspension stability of the system is more difficult to control because of the addition of lightning material. Especially under the condition of large temperature differences, the relative motion between solid particles with large density differences increases, which will aggravate the instability of the slurry and affect the cementing quality. Therefore, to effectively control the suspension stability of the low‐density cementing slurry system, the suspension stabilizer PAND was synthesized by free radical solution polymerization withN‐vinyl caprolactam (NVCL); 2‐acrylamide‐2‐methyl propane sulfonic acid (AMPS),N, N‐dimethyl acrylamide (DMAA) as monomers. The effect of PAND on the stability of low‐density cement slurry under a large temperature difference (40 ~ 120°C) was evaluated. The results showed that under 40 ~ 120°C, adding 0.8% PAND can control the water separation of the cement slurry to 0; the density difference between the upper and lower parts of the cement stone column after curing is less than 0.01 g/cm3. The mechanical properties of cement stone are improved, which shows that it has a good suspension stability effect on low‐density cement slurry systems. The analysis of UV spectroscopy and scanning electron microscopy showed that PAND formed an intermolecular hydrophobic association network structure with the increase in temperature, which could maintain the viscosity of the solution system, thus playing an influential suspension stability role.

Synthesis and Evaluation of Finasteride-Loaded HPMC-Based Nanogels for Transdermal Delivery: A Versatile Nanoscopic Platform.

Herein, we report nanogels comprising diverse feed ratio of polymer hydroxypropyl methylcellulose (HPMC), monomer acrylic acid (AA), and cross-linker methylene bisacrylamide (MBA) fabricated for transdermal delivery of finasteride (FIN). Free radical solution polymerization method with subsequent condensation was employed for the synthesis using ammonium per sulfate (APS) and sodium hydrogen sulfite (SHS) as initiators. Carbopol-940 gel (CG) was formulated as assisting platform to deliver FIN nanogels transdermally. Developed formulations were evaluated by several in vitro, ex vivo, and in vivo parameters such as particle size and charge distribution analysis, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffractogram (XRD), rheological testing, in vitro swelling and drug release, and ex vivo skin permeation, irritation, and toxicity assessment. The results endorsed the nanogel formation (117.3 ± 29.113 nm), and the impact of synthesizing method was signified by high yield of nanogels (≈91%). Efficient response for in vitro swelling and FIN release was revealed at pH 5.5 and 7.4. Skin irritation and toxicity assessment ensured the biocompatibility of prepared nanocomposites. On the basis of the results obtained, it can be concluded that the developed nanogels were stable with excellent drug permeation profile across skin.

Development of compartment model for inhibition of thermal runaway in free-radical polymerization

Shortstopping reactions via injection of chemical inhibitors is a promising technique of emergency response to prevent thermal runaway, with unique advantages of cost effectiveness and process sustainability over current evacuation practices. However, computational modeling of the inhibition process for ensuring successful designs remains challenging. In this paper, a compartment model is developed to investigate the design of the inhibition system with detailed characterization in both complex kinetic mechanism and nonideal mixing effect. The reactor volume is divided into a network-of-zones (NoZ), with each zone modeled as a well-mixed reactor. The free-radical solution polymerization of methyl methacrylate (MMA) in a stirred batch reactor is used as a demonstrative example. The flow parameters and network structure of compartment models are validated with the CFD simulation. The developed compartment models are employed to investigate interactions of poor mixing and exothermic chemistry that lead to thermal runaway and key design factors including injection location, quantity, kinetic requirement, and timing on the effectiveness of quenching thermal runaway.

Corrosion protection properties of poly((benzoyl phenyl) methacrylate-co-methoxy ethylmethacrylate) coating on mild steel

The copolymer, poly(BPM-CO-MOEMA) has been synthesized from different monomer feed ratios of benzoylphenyl methacrylate (BPM) and methoxyethyl methacrylate (MOEMA) was achieved using the free radical solution polymerization technique. The thermal stability of the synthesized copolymers was studied by using TGA and DSC. The molecular weight of the copolymer was determined by GPC. The corrosion protection efficiency of the mild steel specimens coated with different mole ratios of the copolymer has been investigated using electrochemical techniques like EIS and potentiodynamic polarization studies in 1 M H2SO4. The observation of electrochemical results confirmed that the copolymer coating shows good protection efficiency for mild steel in the corrosive media. The surface and morphological investigations also confirm the barrier effect of the copolymer film on the metal surface against the invasion of corrosive ions.