粘接剂和牙本质相互作用机理的傅里叶变换拉曼光谱研究

粘接剂和牙本质之间的相互作用机理,存在机械作用学说和机械化学联合作用学说。本实验运用傅里叶变换拉曼光谱(FT-Ram an),对粘接剂和牙本质的机械化学联合作用机理进行进一步的研究。两类粘接系统共5种粘接剂,分别作用在牙本质表面,然后选用合适的溶剂对经粘接剂作用后的牙本质进行洗涤和浸泡,以便尽量除去物理吸附在牙本质表面的粘接剂。从残留在牙本质表面上粘接剂的光谱变化,观察粘接剂和牙本质相互作用的程度。运用FT-Ram an仪记录从未经任何处理的原始牙本质到最后经过洗涤、浸泡后的各个不同阶段的牙本质的光谱。用经过浸泡后牙本质的FT-Ram an光谱减去原始牙本质的拉曼光谱,得到差减拉曼光谱,并且与原始粘接剂的光谱进行对照,探讨牙本质粘接剂与牙本质表面相互作用机理。实验结果表明:粘接剂与牙本质之间有氢键作用存在。     

Characteristics and Bond Performance of Wood Adhesive Made from Natural Rubber Latex and Alkaline Pretreatment Lignin

The aim of this study was to characterize an aqueous polymer isocyanate (API) type adhesive made from natural rubber latex (NRL) and lignin as base polymers, and to evaluate bond performance of the adhesive as laminated wood adhesive. The base polymers of the adhesive were prepared by blending NRL, polyvinyl alcohol (PVA), and lignin isolated from black liquor of alkaline pretreatment of oil palm empty fruit bunch (OPEFB) and sugarcane bagasse (SB) with compositions of 25/25/0, 25/20/5, 25/15/10, 25/10/15, 25/5/20, and 25/0/25 (w/w/w). The isocyanate crosslinker was added at the level of 15% of the weight of base polymer. The glass transition temperature (Tg), heat degradation, and the homogenity of the adhesive blend were analyzed. The adhesive was used for producing laminated wood (20×8 cm²). Results showed that the addition of lignin in the base polymer blends of API adhesive did not significantly affect the Tg of the adhesives. However, it affected the thermal decomposition and bond performance of the adhesives. There were more residues and less homogenous adhesive solution due to the addition of lignin in the base polyemr blends of API adhesives. The addition of lignin in the base polymer blends caused significant decrease in bond performance of the adhesive applied in glue laminated wood.     

Effects of Alcell Lignin Methylolation and Lignin Adding Stage on Lignin-Based Phenolic Adhesives

To investigate the effects of lignin methylolation and lignin adding stage on the resulted lignin-based phenolic adhesives, Alcell lignin activated with NaOH (AL) or methylolation (ML) was integrated into the phenolic adhesives system by replacing phenol at various adhesive synthesis stages or directly co-polymerizing with phenolic adhesives. Lignin integration into phenolic adhesives greatly increased the viscosity of the resultant adhesives, regardless of lignin methylolation or adding stage. ML introduction at the second stage of adhesive synthesis led to much bigger viscosity than ML or AL introduction into phenolic adhesives at any other stages. Lignin methylolation and lignin adding stage did not affect the thermal stability of lignin based phenolic adhesives, even though lignin-based adhesives were less thermally stable than NPF. Typical three-stage degradation characteristics were also observed on all the lignin-based phenolic adhesives. Three-ply plywoods can be successfully laminated with lignin based adhesives, and it was interesting that after 3 h of cooking in boiling water, the plywoods specimens bonded with lignin-based phenolic adhesives displayed higher bonding strength than the corresponding dry strength obtained after direct conditioning at 20 °C and 65% RH. Compared with NPF, lignin introduction significantly reduced the bonding strength of lignin based phenolic adhesives when applied for plywood lamination. However, no significant variation of bonding strength was detected among the lignin based phenolic adhesives, regardless of lignin methylolation or adding stages.     

Molecular and nanoscale factors governing pressure‐sensitive adhesion strength of viscoelastic polymers

Pressure‐sensitive adhesives (PSAs) are finding increasing applications in various areas of industry and medicine. PSAs are a special class of viscoelastic polymers that form strong adhesive joints with substrates of varying chemical nature under application of light external bonding pressures (1–10 Pa) over short periods of time (1–5 s). To be a PSA, a polymer should possess both high fluidity under applied bonding pressure, to form good adhesive contact, and high cohesive strength and elasticity, which are necessary for resistance to debonding stresses and for dissipation of mechanical energy at the stage of adhesive bond failure under detaching force. For rational design of novel PSAs, molecular insight into mechanisms of their adhesive behavior is necessary. As shown in this review, strength of PSA adhesive joints is controlled by a combination of diffusion, viscoelastic, and relaxation mechanisms. At the molecular level, strong adhesion is the result of a narrow balance between two generally conflicting properties: high cohesive strength and large free volume. These conflicting properties are difficult to combine in a single polymer material. Individually, high cohesive interaction energy and large free volume are necessary but insufficient prerequisites for PSA strength. Evident correlations are observed between the adhesive bond strengths of different PSAs, and their relaxation behaviors are described by longer relaxation times. Innovative PSAs with tailored properties can be produced by physical mixing of nonadhesive long‐ and short‐chain linear parent polymers, with groups at the two ends of the short chains complementary to the functional groups in the recurring units of the long chains. Although chemical composition and molecular structure of such innovative adhesives are unrelated to those of conventional PSAs, their mechanical properties and adhesive behaviors obey the same general laws, such as the Dahlquist's criterion of tack. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Mechanism of adhesion of polyurethane/polymethacrylate simultaneous interpenetrating networks adhesives to polymer substrates

Polyether-based polyurethane/poly (methyl methacrylate-co-ethyleneglycol dimethacrylate) interpenetrating polymer networks [PU/P (MMA–co–EGDMA)-IPNs] were synthesized and used as adhesives to adhere vulcanized natural rubber (NR) and soft polyvinyl chloride (PVC). The structure and morphology of the IPN adhesives in bulk and near the adhesive/substrate interfaces were investigated. A new mechanism of adhesion called conjugate interpenetration of networks across interfaces, which is suitable for IPN adhesives and polymer substrates, was put forward. According to this mechanism, while forming simultaneous interpenetrating networks in the adhesive, the monomers in the IPN adhesive can permeate polymer substrates and polymerize in situ to form gradient IPNs, thereby producing conjugate three-component IPNs near the adhesive/substrate interfaces. It is the conjugate interpenetration of the networks across the interfaces that strengthens interfacial combination remarkably and results in high bond strength of IPN adhesives. © 1994 John Wiley & Sons, Inc.     

Adsorption and conformation of carboxymethyl cellulose at solid-liquid interfaces using spectroscopic, AFM and allied techniques

Carboxymethyl cellulose (CMC) is a polysaccharide which is widely used in many industrial sectors including food, textiles, paper, adhesives, paints, pharmaceutics, cosmetics and mineral processing. It is a natural organic polymer that is non-toxic and biodegradable. These properties make it ideal for industrial applications. However, a general lack of understanding of the interaction mechanism between the polysaccharides and solid surfaces has hindered the application of this polymer. In this work, adsorption of CMC at the solid-liquid interface is investigated using adsorption and electrophoretic mobility measurements, FTIR, fluorescence spectroscopy, AFM and molecular modeling. CMC adsorption on talc was found to be affected significantly by changes in solution conditions such as pH and ionic strength, which indicates the important role of electrostatic force in adsorption. The pH effect on adsorption was further proven by AFM imaging. Electrokinetic studies showed that the adsorption of CMC on talc changed its isoelectric point. Further, molecular modeling suggests a helical structure of CMC in solution while it is found to adsorb flat on the solid surface to allow its OH groups to be in contact with the surface. Fluorescence spectroscopy studies conducted to investigate the role of hydrophobic bonding using pyrene probe showed no evidence of the formation of hydrophobic domains at talc-aqueous interface. Urea, a hydrogen bond breaker, markedly reduced the adsorption of CMC on talc, supports hydrogen bonding as an important factor. In FTIR study, the changes to the infrared bands, associated with the CO stretch coupled to the CC stretch and OH deformation, were significant and this further supports the strong hydrogen bonding of CMC to the solid surface. In addition, Langmuir modeling of the adsorption isotherm suggests hydrogen bonding to be a dominant force for polysaccharide adsorption since the adsorption free energy of this polymer was close to that for hydrogen bond formation. All of the above results suggest that the main driving forces for CMC adsorption on talc are a combination of electrostatic interaction and hydrogen bonding rather than hydrophobic force.     

一种长链叔胺pH敏感抗菌牙体修复材料的合成与抗菌性能

口腔粘结剂常被用于粘结复合树脂和牙本质或牙釉质,但由于残留细菌会导致继发龋病从而使得粘结剂修复体不能提供长期疗效,目前市场上使用的粘结剂均无法避免细菌滋生。本文采用两步法合成了一种甲基丙烯酸酯基封端的长链叔胺,通过柱层析进行纯化,其结构经¹H NMR和FT-IR表征,并对其抗菌性能进行了研究。结果表明：该材料可通过质子化作用提升口腔pH值抑制细菌滋生。     

葡萄球菌肠毒素B分子印迹聚合物的制备及其与蛋白质的结合性能

以葡萄球菌肠毒素B(SEB)蛋白为模板分子,以聚苯乙烯微球为基质,采用表面分子印迹法制备了SEB分子印迹聚合物.利用平衡吸附试验分析了SEB聚合物对目标蛋白的吸附能力及对类似底物的选择性;分析了该聚合物的吸附动力学,并利用扫描电镜观察了其形貌特征和颗粒尺寸.结果表明,经Scatchard模型分析求得的标题聚合物的最大表观结合量Qmax为3.23mg/g;所制备的SEB分子印迹聚合物呈微球形,粒径约为1²μm,对SEB蛋白具有较好的吸附性和特异选择性.     

The surface and interfacial chemistry of polyimide films

The surfaces of polyimide films and the structure just below the surfaces have been extensively studied as people have sought to improve and understand the key factors controlling adhesion. Treatments of all types from primers to plasma etching to sand blasting have been evaluated with varying efforts depending on the application. In recent years, the emphasis has been on understanding the chemical and morphological changes effected by these treatments and then correlating chemistry and morphology with adhesion. The picture that emerges is that surface energy alone, as is the case with most polymers, usually is insufficient to predict adhesion to polyimides. Instead, initial bond strength and bond durability, whether with adhesives or metals directly deposited on the film, depend on chemical bonding, diffusion between deposited layers and the polyimide, formation of a micro composite region controlled in part by topography and the viscoelastic properties of the polymer below the surface. Poor viscoelastic behavior frequently is characterized as a weak boundary layer. Recent work has shown that small amounts of organometallics that diffuse to the surface during the film forming process can significantly affect bondability both to adhesives and to vacuum deposited metals. The possible effect of these additives on bond formation, viscoelastic properties, diffusion and topography is under investigation and will be discussed along with an over view of the primary film forming steps that might affect surface chemistry and structure.     

Preparation and properties of sol–gel waterborne polyurethane adhesive

Waterborne polyurethane (WBPU) sol–gel adhesives were prepared through a prepolymer process followed by a sol–gel reaction of (3-aminopropyl)triethoxysilane (APTES). The terminal amine group of APTES reacted with the NCO group of the prepolymer, and the ethoxy group created Si–O–Si branching by hydrolysis and condensation reactions in water at the dispersion step. Water swelling (%), tensile strength and Young’s modulus of the synthesized WBPU sol–gel adhesives were improved by increasing APTES content. Synthesized WBPU sol–gel adhesives were used for bonding nylon fabrics. A significant improvement in adhesive strength was recorded, and the potential for good adhesive strength under water at moderately high temperature (up to 75 °C) was observed with 6.84 mol% APTES in WBPU sol–gel adhesives.     

Mechanical and chemical analysis of plasma and ultraviolet-ozone surface treatments for thermal bonding of polymeric microfluidic devices

Here we have demonstrated that radio frequency plasma and ultraviolet-ozone (UVO) surface modifications are effective treatments for enabling the thermal bonding of polymeric microfluidic chips at temperatures below the T(g) (glass transition temperature) of the polymer. The effects of UVO and plasma treatments on the surface properties of a cyclic polyolefin and polystyrene were examined with X-ray photoelectron spectroscopy (XPS), contact angle measurements, atomic force microscopy (AFM) surface roughness measurements and surface adhesion measurements with AFM force-distance data. Three-point bending tests using a dynamic mechanical analyzer (DMA) were used to characterize the bond strength of thermally sealed polymer parts and the cross-sections of the bonded microchannels were evaluated with scanning electron microscopy (SEM). The experimental results demonstrated that plasma and UVO surface treatments cause changes in the chemical and physical characteristics of the polymer surfaces, resulting in a decrease in T(g) at the surface, and thus allowing the microfluidic chips to be effectively bonded at temperatures lower than the T(g) of the bulk polymer without losing the intended channel geometry.     

ELASTOMERIC REACTIVE MICROGELS AS TOUGHENER FOR EPOXY ADHESIVES

Elastomerie reactive microgels were evaluated as toughener for epoxy adhesives. It turned out that elastomeric microgels can improve lap shear strength and peel strength greatly. The glass transition temperature of the resin matrix was not affected by the presence of dispersed mierogel particles, and thus the microgel-toughened adhesives have a good bond strength at elevated temperatures.     

A comparison of the strength of autohesion of plasma treated amorphous and semi‐crystalline PEEK films

Polyether ether ketone (PEEK) is a promising material for the encapsulation of electronic components for medical implants but a strong and hermetic joining technology is required. Autohesion is a self‐bonding method that avoids the need for adhesives. The strengths of autohesive joins using amorphous and semi‐crystalline PEEK films after surface activation using RF plasma were compared. Both types of PEEK films showed successful autohesion after activation with the bond strength of the amorphous sample being twice as high as the bond strength of the semi‐crystalline sample. Plasma treatment increased the autohesion strength of PEEK with no observed change in surface roughness (as measured by profilometer). The water contact angle was reduced by the treatment. X‐ray photoelectron spectroscopy (XPS) was carried out to determine surface chemistry. In the case of the semi‐crystalline surface, plasma treatment increased the relative percentage of C? O functional groups compared to the untreated surface. For treated surfaces nitrogen concentration correlated positively with bond strength while oxygen concentration correlated negatively with the semi‐crystalline PEEK samples and positively with the amorphous PEEK samples. The oxygen groups most likely are formed after the treatment by ambient oxidation are not conducive to bond formation, possibly because of the quenching of radicals that would otherwise form links. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of polymerizable poly(alkenoic acid)s via reversible addition fragmentation transfer polymerization for dental applications

The novel polymerizable poly(alkenoic acid)s 1a–1c (expected = 2500, 5000, and 10,000 g/mol) were synthesized in three steps starting from tert‐butyl acrylate. A RAFT polymerization using 2,2‐(thiocarbonylbis(sulfanediyl))bis(2‐methylpropanoic acid) 4 as a chain transfer agent, followed by a Mitsunobu esterification and a deprotection of the tert‐butyl ester groups with trifluoroacetic acid, provided the desired acidic polymers in moderate to good yields. The synthesized polymers were characterized by ¹H NMR spectroscopy and by gel permeation chromatography. The number‐average molecular weights measured for 1a–1c were in good agreement with the expected values. Self‐etch adhesives (SEAs) based on poly(alkenoic acid)s 1a–1c were formulated in order to investigate their adhesive properties. The addition of 1a–1c to a SEA formulation containing 10‐methacryloyloxydecyl dihydrogen phosphate resulted in a strong increase of the shear bond strength (SBS) of a dimethacrylate‐based composite to dentin. No significant influence of the polymer molecular weight on the dentin and enamel SBS was observed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1814–1821     

Estimation of polymer-surface interfacial interaction strength by a contact AFM technique

Atomic force microscopy (AFM) measurements were employed to assess polymer-surface interfacial interaction strength. The main feature of the measurement is the use of contact-mode AFM as a tool to scratch off the polymer monolayer adsorbed on the solid surface. Tapping-mode AFM was used to determine the depth of the scraped recess. Independent determination of the layer thickness obtained from optical phase interference microscopy (OPIM) confirmed the depth of the AFM scratch. The force required for the complete removal of the polymer layer with no apparent damage to the substrate surface was determined. Polypropylene (PP), low-density polyethylene (PE), and PP-grafted-maleic anhydride (PP-g-ma) were scraped off silane-treated glass slabs, and the strength of surface interaction of the polymer layer was determined. In all cases it was determined that the magnitude of surface interaction force is of the order of van der Waals (VDW) interactions. The interaction strength is influenced either by polymer ability to wet the surface (hydrophobic or hydrophilic interactions) or by hydrogen bonding between the polymer and the surface treatment.     

Reliability of liquid crystal cell and immiscibility between dual-curable adhesives and liquid crystal

The dual-curable adhesive used to attach thin film transistors (TFTs) to color filters in the construction process of liquid crystal display (LCD) panels requires fast curing by UV irradiation and strong bond strength after thermal-curing. In addition, it is necessary to consider the immiscibility of the dual-curable adhesives with the liquid crystal, because they come directly into contact with the liquid crystal without curing process in the large LCD panel production. In this study, dual-curable adhesives based on partially acrylated epoxy acrylate oligomers were prepared and investigated with nematic liquid crystals using gas chromatography (GC), polarized optical microscopy and the measurement of the transmittance of the liquid crystal.As the concentration of CC bonds was increased, the immiscibility was enhanced due to the fast curing rate of the partially acrylated epoxy acrylate oligomers and reduced visual contamination was observed in the polarized optical microscope images. Moreover, the transmittance of the liquid crystal cells was not changed before and after the dual-curing of the adhesives and was maintained for 100 h.     

A reversible water-based electrostatic adhesive

Commercial adhesives typically fall into two categories: structural or pressure sensitive. Structural glues rely on covalent bonds formed during curing and provide high tensile strength whilst pressure-sensitive adhesives use physical bonding to provide weaker adhesion, but with considerable convenience for the user. Here, a new class of adhesive is presented that is also reversible, with a bond strength intermediate between those of pressure-sensitive and structural adhesives. Complementary water-based formulations incorporating oppositely charged polyelectrolytes form electrostatic bonds that may be reversed through immersion in a low or high pH aqueous environment. This electrostatic adhesive has the advantageous property that it exhibits good adhesion to low-energy surfaces such as polypropylene. Furthermore, it is produced by the emulsion copolymerization of commodity materials, styrene and butyl acrylate, which makes it inexpensive and opens the possibility of industrial production. Bio-based materials have been also integrated into the formulations to further increase sustainability. Moreover, unlike other water-based glues, adhesion does not significantly degrade in humid environments. Because such electrostatic adhesives do not require mechanical detachment, they are appropriate for the large-scale recycling of, e.g., bottle labels or food packaging. The adhesive is also suitable for dismantling components in areas as varied as automotive parts and electronics.     

Interfacial interactions and the polymer/polyurethane bond

Lap shear measurements of adhesion in joints of polymers bonded with polyurethane adhesives varied significantly with time at elevated temperature. The effect has been linked with the ability of polyurethane molecules to restructure in response to the orienting strength of substrate surfaces, as defined by their non-dispersive surface energy component. Acid/base interactions at the polymer/adhesive interface further affect the bond strength, increasing this important property when acid/base pairs are located at the interface, and diminishing the variable when acid/base interactions are absent.     

Simulation of Polymer Aggregates as a Method to Investigate the Solvent Effect on Blend Complexation and the Relative Strength of H‐Bonding Groups in Blends

Simulations of polymer‐solvent and polymer‐polymer aggregates, in which the study of hydrogen bonding plays an important role, have been carried out with two blend systems. The aim was to examine the influence of the solvent on blend complexation and to compare the strength of different hydrogen bonds in a blend system. We quantified the strength of one hydrogen bond in the blend environments. For this we used the EVOCAP software, developed by our institute. It allows the building of large molecular aggregates with realistic and homogeneous densities, with an implemented positioning algorithm of the molecules under consideration and their excluded volume, and a charge equilibration method for the partial charge calculation. In the simulated aggregates the specific interaction energy of the hydrogen atom forming the hydrogen bond was a useful indicator for our studies. Through a direct correlation of this specific‐interaction energy with the strength of the hydrogen bond, we supported the experimental result that, in toluene, complex formation between poly(methyl methacrylate) (PMMA) and PSOH, a hydroxyl‐modified polystyrene, is possible, but not in tetrahydrofuran. Varying the proton‐donor polymer, also a hydroxyl‐modified polystyrene, in blends of poly(vinyl methyl ether) (PVME) with groups of different donor strength, we reconstructed the experimental row of increasing hydrogen‐bond strengths.     

Interfacial design in fiber reinforced polymers

Different interphases have been created with different film formers and coupling agents on glass and carbon single filaments embedded in thermoplastic and thermosetting matrices. Three micromechanical procedures (pull‐out test, fragmentation test and a version of microbond test in which crack propagation was continuously monitored by optical microscopy) were used to measure fiber/matrix interfacial bond strengh. The effect of interphase microstructure, transcrystallinity as well as matrix molecular weight on the measured bond strength, failure mode, and local properties of the interphase was examined. The possibilities of controlling bond strength between fiber surface and polymer matrix are discussed.