Study of action mechanisms and properties of Cr^(3+) cross-linked polymer solution with high salinity

Performance characteristics of partially hydrolyzed polyacrylamide （HPAM） and cross- linked polymer （CLP, Cr^3＋ as the cross linker） solutions have been investigated. A Brookfield viscometer, rheometer, dynamic light scattering system, and core flow device have been used to measure the viscosity, viscoelasticity, polymer coil dimensions, molecular configuration, flow characteristics, and profile modification. The results show that, under conditions of high salinity and low HPAM and Cr^3＋ concentrations, cross-linking mainly occurred between different chains of the same HPAM molecule in the presence of Cr^3＋, and a cross-linked polymer （CLP） system with a local network structure was formed. Compared with an HPAM solution of the same concentration, the apparent viscosity of the CLP solution increased slightly or remained almost unchanged, but its viscoelasticity （namely storage modulus, loss modulus, and first normal stress difference） increased, and the resistance coefficient and residual resistance coefficient increased significantly. This indicates that the CLP solution exhibits a strong capability to divert the sequentially injected polymer flood from high-permeability zones to low- permeability zones in a reservoir. Under the same HPAM concentration conditions, the dimensions of polymer coils in the CLP solution increased slightly compared with the dimensions of polymer coils in HPAM solution, which were smaller than the rock pores, indicating that the cross-linked polymer solution was well adapted to reservoir rocks. Core flood experiments show that at the same cost of reagent, the oil recovery by CLP injection （HPAM-1, Cr^3＋ as the cross linker） is 3.1% to 5.2% higher than that by HPAM- 2 injection.

Corneal collagen cross-linking in patients with keratoconus from the Dresden protocol to customized solutions:theoretical basis

Keratoconus is an ectatic condition characterized by gradual corneal thinning,corneal protrusion,progressive irregular astigmatism,corneal fibrosis,and visual impairment.The therapeutic options regarding improvement of visual function include glasses or soft contact lenses correction for initial stages,gas-permeable rigid contact lenses,scleral lenses,implantation of intrastromal corneal ring or corneal transplants for most advanced stages.In keratoconus cases showing disease progression corneal collagen crosslinking(CXL)has been proven to be an effective,minimally invasive and safe procedure.CXL consists of a photochemical reaction of corneal collagen by riboflavin stimulation with ultraviolet A radiation,resulting in stromal crosslinks formation.The aim of this review is to carry out an examination of CXL methods based on theoretical basis and mathematical models,from the original Dresden protocol to the most recent developments in the technique,reporting the changes proposed in the last 15y and examining the advantages and disadvantages of the various treatment protocols.Finally,the limits of non-standardized methods and the perspectives offered by a customization of the treatment are highlighted.

Self-assembling Behavior of Amphiphilic Copolymer Containing Cross-linked Hydrophilic Block in Ethanol

The self-assembly behavior of the amphiphilic block copolymer poly（ methyl methacrylate） -block-poly（ lead dimethacrylate） （PMMA-b-PLDMA） with cross-linked hydrophilic block（PLDMA） in ethanol was investigated. The results show that the size and morphology of the resulting micelle or micellar aggregates are ascribed to the content of ethanol and the nature of the solvent mixture. PbS nanoparticles were formed in the micelle by in situ reaction with H2S gas. The morphology and size of the self-assembly objects were investigated using scanning electron microscopy （SEM） and transmission electron microscopy（TEM）.

The effect of cations on gelation of cross-linked polymers

The effects of different cation concentrations and types on rheological property and stability of Guar, Xanthan, and Partially Hydrolyzed Polyacrylamide(HPAM) cross-linked gels were analyzed through experiments. Also, a new approach was developed to reduce the negative effects of cation by application of multi-walled carbon nano-tubes(MWCNTs). The presence of cations in cross-linked gel system will reduce the viscosity of gel, the higher the cation concentration is, the lower the viscosity will be. The bivalent cation has a greater viscosity reduction effect on gel than monovalent cation. The stability of cross-linked gels is worse with cations, this situation becomes more serious under higher salinity. MWCNTs were added to HPAM gel, cross-linked by(3-Aminopropyl) triethoxysilane(APTES), they surrounded cations and removed them from polymers and reduced the reaction possibility. This method enhances the viscosity and breakdown pressure of cross-linked gels, improves the stability of HPAM cross-linked gel under different operating conditions, and can be applied to related drilling projects.

Self-Cross-Linked Tannin-Aminated Tannin Surface Coatings for Particleboard

Aminated tannins were prepared by reacting mimosa condensed tannin extract with ammonia yielding the substitution of many,if not all of the tannin hydroxyl groups with–NH_(2)groups.A tannin-aminated tannin(ATT)particleboard coating was then prepared by reacting raw tannin extract with aminated tannin extract and thus cross-linking the two by substituting tannin’s hydroxyl groups with the–NH_(2)groups on the aminated tannin to form–NH-bridges between the two.The resulting particleboard coating gave encouraging results when pressed at 180℃for 3 min.Conversely,the system in which tannin was reacted/cross-liked with urea(ATU)by a similar amination reaction did not perform as well as the ATT system,and this even when a higher curing temperature and longer hot press time were used.In particular its water repellence was worse probably due to the presence of urea and such a system with lower reactivity.Nonetheless,substituting the tannin–OHs with the urea–NH_(2)groups appeared to also take place.ATT gave better results than ATU as regards water repellence and mechanical resistance as shown by the cross cut test.The ATT system was shown to be between 95%and 98%biosourced.The difference appeared to be due,by TMA analysis,to the much faster formation of the ATT hardened network leading to a better cross-linked polymer coating.The chemical species formed for both the ATT and ATU system were studied by MALDI ToF and CP MAS^(13)C NMR.

Influence of dissolved oxygen content on oxidative stability of linked polymer solution

The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at the same temperature, the degree of the oxidative degradation of the LPS increased and the rapidity of the oxidative degradation was accelerated with the increase of the dissolved oxygen content. Consequently, the size of linked polymer coils (LPCs) of the LPS became small, and the plugging capability of the LPS decreased. At a fixed content of dissolved oxygen, with increasing degradation temperature, almost the same results were observed, namely, an increased degree of oxidative degradation, accelerated rapidity of the oxidative degradation and decreased plugging capacity, with decreased oxidative stability of LPS. At 90 °C, in the presence of oxygen, LPS lost its plugging capability after having been degraded for a period of time. But at 40 °C, LPS with low dissolved oxygen content could be stable for a long time. The decreased plugging ability of LPS after oxidative degradation is mainly caused by the decreased size and number of the LPCs due to the breaking of hydrolyzed polyacrylamide (HPAM) molecule segments and the structural changing of HPAM molecules.

Deformation of Linked Polymer Coils

Linked polymer solution (LPS) is defined as the solution of linked polymer coils (LPCs) dispersed in water, composed of low concentration partially hydrolyzed polyacrylamide (HPAM) and aluminum citrate (crosslinker). In the work, the conformational changes of LPCs under different conditions were investigated by the methods of membrane filtering under low pressure, dynamic light scattering and core flooding experiments. The results showed that in some conditions the LPCs could be compressed mechanically to 1/158.5 of their original volume because of relatively lower HPAM cross-linking. The hydration property of LPCs was similar to that of normal polymer coils. The deformation of LPCs was more restricted than that of ordinary polymer coils under the flow shear stress or the shift of hydration equilibrium caused in the variation of the electrolyte concentration which is responsible for the effective plugging in the throats of porous media when LPCs are used for deep diverting.

A NOVEL POLYMER ENZYME LINKED IMMUNOASSAY METHOD AND ITS APPLICATIONS

During the course of study, we found that both poly (N-isopropylacrylamide ) (PNIP) and PNIP-Ab (enzyme-labelled antibody)could be adhere tightly to a cellulose acetale-nitrate membrane, and that the retention of PNIP-Ab on the membrane increased over 30-fold when compared with the unconjugated Ab.Thus we used this characteristic to develop a novel immunoassay method-polymer enzyme linked immunoassay method: homogeneous antigen-antibody reaction and heterogeneous separation process. When applied for detection of human serum HBsAg, this immunoassay system can detect as little as 1 ng/ml of human serum HBsAg.

Contactless Raman Spectroscopy-Based Monitoring of Physical States of Silyl-Modified Polymers during Cross-Linking

Cross-linking of silyl-modified polymers occurs at the alkoxysilane groups attached to the ends of polymer chains by hydrolysis and polycondensation mechanisms in the presence of moisture. During these reactions, three different physical states can be identified (viscous, skin effect and cross-linked state). Knowledge of the evolution of these states at each reaction time is essential to determine the open time for the adhe-sive industry and is generally obtained by a manual method. Automation of this moni-toring could avoid operator error and could be used for very long cross linking reac-tions or to screen a large number of catalysts. Thus, a contactless micro process tech-nology was developed to correlate these physical states with an optical technology, Raman spectroscopy, by monitoring the decrease in intensity of the Si-OCH3 groups during chemical reactions. This online characterization method can also be used to compare the efficiencies of several catalysts for the cross-linking of silyl-modified polymers, using a minimum amount of chemical materials.

Applications of Crown Ether Cross-Linked Chitosan for the Analysis of Lead and Cadmium in Environmental Water Samples

A new type of crown ether cross-linked chitosan was synthesized by the reaction of chitosan with 4,4′-dibromodibenzo-18-crown-6 (Br-DBC). Its token structure was analyzed with FT-IR and NMR and the adsorption behaviors for lead and cadmium in environmental water samples by FAAS were studied. In addition the best analysis conditions were discussed and the adsorption mechanism was explained. As the enrichment factor is above 100, both recoveries are 94%–106%, the detection limits of lead and cadmium are 0.5μg·L?1 and 0.04 μg·L?1 and the relatively standard deviations of lead and cadmium are 3.1% and 2.8% respectively, this new method was successfully applied to the determination of environmental water samples. This method is fast and simple and it greatly enhances the determination ability of FAAS for lead and cadmium.

Study on the Structure of Peroxide Cross-Linked Polyethylene Pipes with Several Stabilizers

Cross-linked polyethylene (PEX) pipes used in hot water supply are required for high mechanical strength and high creep resistance at high temperature. Especially PEX-a pipes which are made by peroxide cross-linking have better performance, such as creep resistance and thermal shock resistance than the pipes made by the other cross-linking method. Because the PEX-a pipes indicate the higher cross-link degree as compared with the other PEX pipes. In this study, the PEX-a pipes which were mixed with several stabilizers were tested to evaluate the effects on cross-link degree and the oxygen induction time. And also they are evaluated with the chlorine aqueous solution by the performance of the long-term hydrostatic pressure test and the long-term hydro dynamic pressure test. As a result, it was found that the combination of antioxidants for PEX-a pipes plays an important role to prolong the oxygen induction time without inhibiting the cross-linking. From the results of the 1H pulsed NMR measurement over the melting point of polyethylene, it was found that each peroxide PEX pipe with different antioxidant combinations indicated the different proportion and crosslink density of cross-linked region, in addition, that these pipes had the effective structure of cross-linking for the hydrostatic and hydrodynamic pressure test with the chlorine aqueous solution. Therefore, it was considered to be useful results for studies of the stricture of cross-linking of polyethylene.

Dynamic Mechanical and Thermal Properties of Cross-linked Polystyrene/Glass Fiber Composites

Cross-linked polystyrene/glass fiber composites were fabricated using cross-linked polystyrene （CLPS） as matrix and E-glass fiber as the reinforcement. Surfaces of E-glass fibers were modified by vinyl triethoxysilane （VTES）, vinyl trimethoxysilane （VTMS） and γ-methacryloylpropyl trimethoxysilane （MPS）. The treated glass fibers were analyzed by fourier transform infrared spectroscopy （FTIR）. Dynamic mechanical thermal analysis （DMTA） and thermo-gravimetric analysis （TGA） were employed to investigate the effect of glass fibers surface modification on viscoelastic behavior and thermal properties. The morphology of fracture surfaces of various composites was observed by scanning electron microscopy （SEM）. The results revealed that these coupling agents were connected to the surfaces of the fibers by chemical bonding. Dynamic mechanical properties as well as thermal stability of the composites were improved considerablely, but to varying degrees depending on the fiber modification. The diversities of improvement of properties were attributed to the different interfacial adhesion between CLPS matrix and the glass fibers.

Fabrication and characterization of cross-linked gelatin electro-spun nano-fibers

In this study, we developed a fast, simple and novel process to fabricate cross-linked electro-spun gelatin with limited amounts of glutaraldehyde (GA) using trifluoroacetic acid (TFA) as the solvent. Using SEM, the uncross-linked gelatin fibers were determined to have diameters between 50-300 nm, while the cross-linked gelatin electro-spun fibers had diameters between 100-500 nm. FT-IR revealed that the un-cross-linked and cross-linked electro-spun gelatin was fabricated successfully by electro-spinning using TFA as a solvent, which has not been reported until now. Stress-strain curves showed that the addition of small amounts of GA increased the strength of the gelatin by two fold and allowed for the creation of a water insoluble gelatin electro-spun membrane.

Preparation and characterization of genipin-cross-linked chitosan microparticles by water-in-oil emulsion solvent diffusion method

Chitosan (CS) microparticles with and without cross-linking were prepared by a water-in-oil emulsion solvent diffusion method without any surfactants. Aqueous CS solution and ethyl ace- tate were used as water and oil phases, respectively. Genipin was used as a cross-linker. Influ- ences of genipin ratios and cross-linking times on CS microparticle characteristics were investigated. Non-cross-linked and cross-linked CS microparticles were spherical in shape and rough in surface. Microparticle matrices showed porous structures. Surface roughness, mean par- ticle sizes and bulk density of CS microparticles increased and their dissolutions in acetic acid solution decreased when genipin ratio and cross- linking time increased.

Pt Deposition on Anode Enhances the Performance of Dye-Sensitized Solar Cell with Non-Cross-Linked Gel Electrolyte

We fabricated dye-sensitized solar cells with non-cross-linked fluorinated gel electrolyte. The application of fluorinated gel to electrolyte is a challenging issue at present. The gelation of the electrolyte is of importance in order to solve the problem in the durability of the cell. We investigated, in this article, the effect of Pt deposition on the anode of the cell. The Pt was deposited by means of a DC sputtering technique. The studies showed that the deposition time strongly affected both open voltage and short-circuit current of the cell. The adaptive thickness of the Pt layer was determined to be 10 nm for the non-cross-linked fluorinated gel electrolyte cells.

Characterization of Ionic Conducting Cross-linked Polyether Electrolytes

An appropriate amount of toluene 2,4-diisocyanate（TDI） was added into polyether（[（CH2CH2O）13 CH2O]n/Li salt electrolyte to form a cross-linked network,with improving the film proces sability and thermal stability.The relation between the structure and ioinc conductive properties of the cross-lined polyether electrolytes was investigated by means of Fourier transform infra-red spectroscopy（FTIR）,differential scanning calorimetry（DSC）,mechanical property and AC impedance spectroscopy.The electrolytes system is found to have two glass transitions,and it is found that the two Tgs increase with increasing salt concentration.At the some Li salt concentration,the conductivity of cross-liked polyether/LiN（CF3SO2）2 complex system is higher than that of LiClo4,At EO/Li=25：1（mol ratio）,the former conductivity changes with temperature,while the later coincids with Arrhenius formula（σ=Ae^-Ea/RT）.The cross-linked polyether/LiN（CF3 SO2）2 electrolyte exhibits the maximum σ=10^-4.75S/cm at 30℃.

Gas permeation properties of a metallic ion-cross-linked PIM-1 thin-film composite membrane supported on a UV-cross-linked porous substrate

Metallic ion-cross-linked polymer of intrinsic microporosity(PIM-1) thin-film composite(TFC) membranes supported on an ultraviolet(UV)-cross-linked porous substrate were fabricated. The UV-cross-linked porous substrate was prepared via polymerization-induced phase separation. The PIM-1 TFC membranes were fabricated via a dip-coating procedure. Metallic ion-cross-linked PIM-1 TFC membranes were fabricated by hydrolyzing the PIM-1 TFC membrane in an alkali solution and then cross-linking it in a multivalent metallic ion solution. The pore size and porous structures were evaluated by low-temperature N_2 adsorption–desorption analysis. The membrane structure was investigated by field-emission scanning electron microscopy. The effects of heat treatment and pore-forming additives on the gas permeance of the UV-cross-linked porous substrate are reported. The effects of different pre-coating treatments on the gas permeance of the metallic ion-cross-linked PIM-1 TFC membrane are also discussed. The metallic ion-crosslinked PIM-1 TFC membrane displayed high CO_2/N_2 selectivity(23) and good CO_2 permeance(1058 GPU).

Swelling Studies of Chitosan-Gelatin Films Cross-Linked by Sulfate

Swelling properties of chitosan-gelatin films cross-linked by sulfate were investigated. Sulfate cross-linked chitosan-gelatin films (SCG) were prepared simply by dipping chitosan-gelatin films into sodium sulfate solution. The swelling behavior of SCG was investigated as a function of pH and ionic strength. Under acidic conditions pH less than 4, SCG swelled less than 120%, while under the conditions pH larger than 7.4, SCG swelled very significantly, the swelling ratio was over 350%. Sodium chloride weakened the electrostatic interaction between sulfate and amine ions of chitosan and gelatin, therefore facilitated the film swelling. The swelling ratio increased with increasing sodium chloride concentration, the SCG dissociated in the sodium chloride concentration of 0.20 mol·L?1. The parameters of film preparation such as sulfate concentration, dipping time, sulfate solution pH, influenced the film swelling behavior. The lower concentration and the higher pH of sulfate solution resulted in a larger swelling ratio. Key words chitosan - gelatin - sulfate cross-linking - swelling CLC number O 636.1 Foundation item: Supported by the National Natural Science Foundation of China (29977014)Biography: Xiao Ling (1964-), female, Associate professor, research direction, biopolymers.

CRYSTALLIZATION AND MELTING OF POLY(ETHYLENE OXIDE)CONFINED IN NANOSTRUCTURED PARTICLES WITH CROSS-LINKED SHELLS OF POLYBUTADIENE

Small fixed aggregates of a poly(ethylene oxide)-block-polybutadiene diblock copolymer(PEO-b-PB)in THFsolution were obtained by adding a selective solvent for PB blocks,followed by cross-linking the PB shells.Themorphologies of the nanostructured particles with a cross-linked shell were investigated by atomic force microscopy andtransmission electron microscopy.The average behaviors of the PEO crystallization and melting confined within thenanostructured particles were studied by using differential scanning calorimetry experiments.For the deeply cross-linkedsample(SCL-1),the crystallization of the PEO blocks was fully confined.The individual nanoparticles only crystallized atvery low crystallization temperatures(T_cs),wherein the homogenous primary nucleation determined the overallcrystallization rate.For the lightly cross-linked sample(SCL-2),the confinement effect was T_c dependent.At T_c(?)42℃,thecrystallization and melting behaviors of SCL-2 were similar to those of the pure PEO-b-PB diblock copolymer.At T_c>42℃,SCL-2 could form PEO lamellae thicker than those of the pure PEO-b-PB crystallized at the same T_c.

Synthesis and Properties of Lactic Acid-based Cross-linked Poly(ester-amide)

A novel lactic acid-based cross-linked poly（ester-amide） （LCPEA） was synthesized. The gel fraction of the LCPEA could be modulated by the reaction conditions and it affected the mechanical and thermal properties of the LCPEA. The tensile strength, elastic modulus and bend strength of the LCPEA of 65% gel fraction were 4.65, 136.55 and 39.63 MPa, respectively. The thermal decomposition temperature （50 wt%） of the LCPEA was around 410℃.