No abstract

Shape memory hydrogels offer the ability to recover their permanent shape from temporarily trapped shapes without application of external forces. Here, we report a novel dual-responsive shape memory hydrogel with characteristic thermoplasticity. The water-insoluble hydrogel is prepared by simple ternary copolymerization of acrylamide (AM) and acrylic acid (AA) with low amounts of a cationic surfmer, in the absence of organic crosslinkers. Through either ionic/complex binding of carboxyl groups via trivalent cations or salt-dependent hydrophobic association, the hydrogel can memorize a temporary shape successfully, which recovers its permanent form in the presence of a reducing agent or deionized water. Besides, the unique thermoplasticity of the hydrophobic polyampholyte hydrogel allows the change of its permanent shape upon heating and the fixation after cooling, which is in strong contrast to the conventional chemically cross-linked shape memory hydrogels. This fascinating feature undoubtedly enriches the shape memory hydrogel systems. Thus, we believe that the facile strategy could provide new opportunities with regard to the design and practical application of stimulus-responsive hydrogel systems.

Pilot tests commenced from 1980s in Daqing Oilfield have proved that ASP flooding could improve the recovery rate by 20% based on water flooding, while scaling issue in producers was the only factor which made it hard to reach that objective. Investigation in site indicated that more than 70 percent producers had scaling issues, and scaling types and degree in ASP producers varied dramatically in different wells and different period. In the peak of scaling period, the averaged running life was only a couple of months. A project focused on the harness of scaling issue in ASP producers was implemented from 2002. In the first stage, the study aimed at getting the scaling principle in ASP producers. A series of monitoring and analysis on producing fluid's ion concentration were implemented in different ASP producers. The scale deposited on tubing in different depths were picked out and analyzed. The scaling mechanism of ASP producing liquids in artificial lift systems were created which presented the varying principle of scaling ions as well as the characteristics of scale in ASP producers. A set of scaling principle prediction plates was also created with a success ratio being above 90%. In the second stage, a series of anti-scaling artificial lift techniques were developed including new anti-scaling pump, chemical scale removers and scale inhibitors, and other matching techniques. The new anti-scaling techniques were put into application from several wells up to near 1,000 wells. The operating rate has been improved by 4.13 percent as well as the operating cost decreased by 72.77%. The technical breakthrough in anti-scaling artificial lift systems improved the operating life of ASP producers considerably. It applied solid foundation for ASP flooding to become a beneficial method for mature oilfield development in commercial scale.

Oxidized sodium alginate is a handily modifiable polysaccharide owing to the pendant aldehyde groups which can form dynamic covalent bonds with amines, acylhydrazines, etc., providing oxidized sodium alginate-based hydrogels with stimuli-responsive properties. However, due to the stiffness and, in particular, the hydrophobicity of sodium alginate dialdehyde at low pH, the mechanical performance and pH stimuli responsiveness of oxidized sodium alginate-based hydrogels are still strictly limited. Herein, we report a new strategy to build an injectable, dual responsive, and self-healing hydrogel based on oxidized sodium alginate and hydrazide-modified poly(ethyleneglycol) (PEG). The hydrazide-modified PEG, referred to as PEG-DTP, acts as a macromolecule crosslinker. We found that the presence of PEG-DTP reduces the hydrophobicity of oxidized sodium alginate at low pH so effectively that even a pH-induced reversible sol-gel transitions can be realized. Meanwhile, the disulfide bonds in PEG-DTP endows the hydrogel with the other reversible sol-gel transitions by redox stimuli. In particular, due to the softness of PEG-DTP chains, mechanical performance was also enhanced significantly. Our results indicate we can easily integrate multi-stimuli responsiveness, injectability, and self-healing behavior together into an oxidized sodium alginate-based hydrogel merely by mixing an oxidized sodium alginate solution with PEG-DTP solution in certain proportions.

A novel thermally sensitive shape memory (SM) hydrogel is prepared by block copoly-merization of a cationic surfactant monomer, dimethylhexadecyl[2-(dimethylamino)ethylmethacrylate]ammoniumbromide (C(16)DMAEMA), and acrylamide (AM) in the presence of α-cyclodextrin (α-CD) using N,N'-methylenebisacrylamide (MBA) as a crosslinker. XRD, solid state (13)C NMR, and DSC measurements show that the crystalline domains, induced by the hydrogen bonds between α-CDs threaded on the hydrophobic units of the polymer chains through the host-guest approach, can reversibly melt and crystallize at different temperatures. Rheological measurements show that both the elastic modulus G' and viscous modulus G'' drastically change due to the formation and dissolution of the crystalline domains. These thermo-sensitive crystalline domains serve as reversible physical crosslinks, endowing the hydrogel with excellent SM properties. Cyclic experiments show that the hydrogel can recover to almost 100% of the deformation in each cycle and can be reused several times.

Smart materials responsible to external stimuli such as temperature, pH, solvents, light, redox agents, and mechanical or electric/magnetic field, have drawn considerable attention recently. Herein, we described a novel rhodamine (Rh) mechanophore-based mechanoresponsive micellar hydrogel with excellent mechanochromic and mechanofluorescent properties. We found with astonishment that, due to the favorable activation of rhodamine spirolactam in the presence of water, together with the stress concentration effect, the mechanoresponsive sensitivity of this hydrogel was enhanced significantly. As a result, the stress needed to trigger the mechanochromic property of Rh in the hydrogel was much lower than in its native polymer matrix reported before. The hydrogel based on Rh, therefore, exhibited excellent mechanochromic property even at lower stress. Moreover, due to the reversibility of color on/off, the hydrogel based on Rh could be used as a reusable and erasable material for color printing/writing. Of peculiar importance is that the hydrogel could emit highly bright fluorescence under sufficient stress or strain. This suggested that the stress/strain of hydrogel could be detected quantificationally and effectively by the fluorescence data. We also found that the hydrogel could respond to acid/alkali and exhibited outstanding properties of acidichromism and acidifluorochromism. Up to now, hydrogels with such excellent mechanochromic and mechanofluorescent properties have rarely been reported. Our efforts may be essentially beneficial to the design of the mechanochromic and mechanofluorescent hydrogels with enhanced mechanoresponsive sensitivity, fostering their potential applications in a number of fields such as damage or stress/strain detection.

UV-controlled shape memory hydrogel is designed with PhotoAcid Generator (PAG) as the trigger.

We report a highly compressible polypseudorotaxane supramolecular hydrogel with antifatigue properties that can bear 80% compressive strain without rupture.