链转移剂O-乙基黄原酸丙酸乙酯的合成

以KOH、CS2和2-溴代丙酸乙酯为原料在无水乙醇中反应合成了一种新型的RAFT聚合链转移剂O-乙基黄原酸丙酸乙酯,通过红外光谱和核磁共振氢谱对其结构进行了表征和分析,确证所制备最终产物为目标产物。     

Relationship between the surface free energy of hardened cement paste and chemical phase composition

Special emphasis is put on to correlating the changes in phase composition with wettability of hardened cement paste. The results were found in contradiction, because it was demonstrated by XRD analysis that by increment in curing ages, high energy products are developed in the matrix which increases surface free energy. In contrast, surface evaporation of the water and bulk hydration cause a decrease in hydrophilic properties of the surface free energy. It was concluded that the latter phenomenon has more important impact than surface free energy.     

Effect of surface free energy on the adhesion of biofouling and crystalline fouling

Pipelines and heat exchangers using seawater as coolant suffer from biofouling. Biofouling not only reduces heat transfer performance significantly, but also causes considerable pressure drop, calling for higher pumping requirements. It would be much more desirable if surfaces with an inherently lower stickability for biofouling could be developed. In this paper, a cost-effective autocatalytic graded Ni-Cu-P-PTFE composite coating with corrosion-resistant properties was applied to reduce biofouling formation. The experimental results showed that the surface free energy of the Ni-Cu-P-PTFE coatings, which were altered by changing the PTFE content in the coatings, had a significant influence on the adhesion of microbial and mineral deposits. The Ni-Cu-P-PTFE coatings with defined surface free energy reduced the adhesion of these deposits significantly. The anti-bacterial mechanism of the composite coatings was explained with the extended DLVO theory.     

Model for seawater fouling and effects of temperature,flow velocity and surface free energy on seawater fouling☆

A kinetic model was proposed to predict the seawater fouling process in the seawater heat exchangers.The new model adopted an expression combining depositional and removal behaviors for seawater fouling based on the Kern–Seaton model.The present model parameters include the integrated kinetic rate of deposition(k d)and the integrated kinetic rate of removal(k r),which have clear physical signi ficance.A seawater-fouling monitoring device was established to validate the model.The experimental data were well fitted to the model,and the parameters were obtained in different conditions.SEM and EDX analyses were performed after the experiments,and the results show that the main components of seawater fouling are magnesium hydroxide and aluminum hydroxide.The effects of surface temperature,flow velocity and surface free energy were assessed by the model and the experimental data.The results indicate that the seawater fouling becomes aggravated as the surface temperature increased in a certain range,and the seawater fouling resistance reduced as the flow velocity of seawater increased.Furthermore,the effect of the surface free energy of metals was analyzed,showing that the lower surface free energy mitigates the seawater fouling accumulation.     

Characterization of cellulose surface free energy

The thin-layer wicking technique was used to determine the surface free energy components and the surface character of three celluloses (Sigmaccll 101, Sigmacell 20, and Avicel 101), using an appropriate form of the Washburn equation. For this purpose, the penetration rates of probe liquids into thin porous layers of the celluloses deposited onto horizontal glass plates were measured. It was found that the wicking was a reproducible process and that the thin-layer wicking technique could be used for the determination of the celluloses' surface free energy components. The size of the cellulose particles was characterized with the Galai CIS-100 system and their crystallinity was measured by X-ray diffraction. The three celluloses have high apolar (y^LWS = 50-56 mJ/m²) and electron donor (γs = 42-45 mJ/m²) components, while the electron acceptor component (γS⁺ ) is practically zero. The free energy interactions of cellulose/water/cellulose calculated from the components are positive, regardless of the cellulose crystallinity. This would mean that the cellulose surfaces have a hydrophilic character. However, the work of spreading of water has a small negative value (3-9 mJ/m²), indicating that the surfaces are slightly hydrophobic. It is believed that the work of spreading characterizes better the hydrophobicity of the surface than the free energy of particle/water/particle interaction, because in the latter case, no electrostatic repulsion is taken into account in the calculations.     

Thermal properties and surface energy characteristics of interpenetrating polyacrylate and polybenzoxazine networks

We have prepared semi-interpenetrating polyacrylate networks (PA/BA-m s-IPNs) through rapid photopolymerization of a triacrylate monomer (TMPTA) in the presence of a photoinitiator (I184), a tetramercaptane transfer agent (4SH), and N-methyl-bisbenzoxazine (BA-m). Next, we prepared novel fully interpenetrating polyacrylate (PA) and polybenzoxazine (PBZ) networks (PA/PBZ f-IPNs) through thermal polymerization of the BA-m monomer at 180 °C for 4 h. For the PA/BA-m s-IPNs, the BA-m monomers can be frozen and dispersed in the UV-cured PA network within 5 min to inhibit macrophase separation. After thermal polymerization, the phenol units of the ring-opened PBZ segments can form a hydrogen-bonding interface with the carbonyl groups to improve the compatibility between the PBZ microdomains and the PA networks. From an analysis using Kissinger's method, the non-isothermal kinetics of the thermal polymerization for the PA/BA-m s-IPNs indicate that an increase in the PA content increased the steric hindrance of PBZ polymerization. We used DSC, TGA, and contact angle analyses to determine the glass transition temperature, thermal stability, and surface free energy, respectively, of the PA/PBZ f-IPNs. The thermal stability and surface free energy of these PA/PBZ f-IPNs display linear relationships with respect to the PBZ content.     

Design for improved adhesion of fluorine-incorporated hydrogenated amorphous carbon on metallic stent: Three-layered structure with controlled surface free energy

Hydrogenated amorphous carbon (a-C:H) or element-incorporated a-C:H have attracted much attention as coating materials on coronary artery stents owing to their outstanding properties. However, their applications have been limited because of poor adhesion to metallic materials. The present work was thus aimed at improving the adhesive property of a-C:H-based film on a stent by introducing interlayers with controlled surface free energies.Here we propose a three-layered coating for a SUS316L stent, comprising fluorine-incorporated a-C:H (a-C:H:F), silicon-incorporated a-C:H (a-C:H:Si), and hydrogenated amorphous silicon carbide (a-SiC:H) layers (from top to bottom). Each layer was deposited using a radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) method, and the surface free energy of each layer was controlled by the experimental parameters. Thereafter, the three-layer-coated stent was expanded and evaluated under a scanning electron microscope (SEM) in order to determine whether or not cracking or delamination had occurred. It can be seen from the SEM images that the occurrence of cracks or delamination was markedly suppressed even in the bent region of the stent after expansion, where the plastic deformation is highly localized when stents are expanded. This indicates that the method we applied in this work can serve as one approach to overcoming the limitation described above.     

(S)-2-(ethyl propionate)-(O-ethyl xanthate)- and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate)-mediated RAFT polymerization of vinyl acetate

(S)-2-(Ethyl propionate)-(O-ethyl xanthate) (X1) and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate) (X2) were used as the reversible addition-fragmentation chain transfer (RAFT) agents for the radical polymerization of vinyl acetate (VAc). The former showed the better chain transfer ability in the polymerization at 60°C. Kinetic study with both RAFT agents showed pseudo-first order kinetics up to around 85% monomer conversion. Molecular weight of the resulting polymer increased linearly with increase in the monomer conversion up to around 85%. The observed molecular weights calculated from ¹H-NMR spectrum [M_n(NMR)] are close to the corresponding theoretical molecular weights [M_n(theor)]. The corresponding polydispersity index (PDI) of the resulting polymers remained almost constant at around 1.2 up to ∼ 65% monomer conversion and then increased gradually with the further increase in the monomer conversion. Chain-end analysis of the resulting polymers by ¹H-NMR showed clearly that polymerization started with the radical forming out of the xanthate mediator. The negligible homo-chain extension and the hetero-chain extension involving synthesis of poly(VAc)-b-poly(NVP) diblock copolymer were occurred. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on the surface free energy and surface structure of PTFE film treated with low temperature plasma

The surface free energy and surface structure of poly(tetrafluoroethylene) (PTFE) film treated with low temperature plasma in O₂, Ar, He, H₂, NH₃, and CH₄ gases are studied. The contact angles of the samples were measured, and the critical surface tension γ_c (Zisman) and γ_c (max) were determined on the basis of the Zisman's plots. Furthermore, the values of nonpolar dispersion force γ^a_s, dipole force γ^b_s, and hydrogen bonding force γ^c_s to the surface tensions for the plasma-treated samples were evaluated by the extended Fowkes equation. Mainly because of the contribution of polar force, the surface free energy and surface wettability of PTFE film which was treated with H₂, He, NH₃, Ar, and CH₄ for a short time increased greatly. Electron spectroscopy for chemical analysis (ESCA) shows that the reason was the decrease of fluorine and the increase of oxygen or nitrogen polar functional group on the surface of PTFE. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1733–1739, 1997     

The synergetic depression effect of KMnO4 and CMC on the depression of galena flotation

The mechanism of carboxymethyl cellulose (CMC) on the galena surface and the enhancement of KMnO₄ on the depression of CMC to galena were investigated by flotation test, surface adsorption experiments, scanning electron microscopy-energy dispersive spectrometry (SEM-EDS), and X-ray photoelectron spectroscopy (XPS). Flotation test results indicated that the addition of KMnO₄ under alkaline condition significantly enhanced the depression effect of CMC on galena. Surface adsorption experiments of butyl xanthate (BX) and CMC demonstrated that the adsorption amount of BX decreased after CMC was added into the pulp. And the adsorption amount of CMC increased while BX decreased sharply when KMnO₄ was added into the pulp. After galena was treated with KMnO₄ and CMC, dim spots (oxidation sites) on the surface of galena were observed by SEM-EDS. Results showed the high contents of C and O on the oxidation sites. XPS results indicated that oxidation-reduction reaction occurred on the mineral surface, and PbS₂O₃ or Pb(OH)₂ was probably the main component of the oxidization sites. The CMC could be adsorbed on the oxidation sites by the hydrogen bond to form a hydrophilic membrane on the mineral surface lead to galena depression. All results showed that KMnO₄ could enhance the depression effect of CMC on galena.     

Relationship between surface chemistry and surface energy of different shape pigment blend coatings

The influence of pigment shapes and pigment blends on the surface energy was investigated and compared with the surface chemistry of pigmented latex coatings. The coatings were made of different volume ratios of two pigments: plate-like kaolin clay pigment and prismatic precipitated calcium carbonate (PCC) pigment. These were mixed together with carboxylated styrene–butadiene–acrylonitrile latex (SBA), and applied over nonabsorbent substrates as well as absorbent substrates. The composition of the surface of the coatings was investigated by X-ray photoelectron spectroscopy (XPS). Two approaches were used to estimate the total surface energy and the components of the coatings: a conventional approach—“the Kaelble approach”—and a more modern approach—“the van Oss approach.” Pigment blends with different shapes and increments caused a change in the surface chemistry and the surface energy of the latex coatings. As the prismatic PCC pigment particles increased in the kaolin/SBA coating system, the SBA latex content at the coating surface increased and the total surface energy of the coating decreased. This is valid for both nonabsorbent as well as absorbent substrates. It was found that there was a strong correlation between the surface energy and the surface composition. The surface energy of the coatings estimated by the Van Oss approach was always lower than that estimated by the Kaelble approach. Colloidal interactions between pigment–pigment and/or pigment–binder were thought to play an essential role in determining the final coating surface energy and its components. Changes in the surface latex content and the surface energy due to the different pigment blends investigated were found to fit straight-line equations.     

过渡状态冷凝传热模型

引入沟流级别的概念解释过渡状冷凝形态的形成特征,并在此基础上,将过渡状冷凝传热表示为通过滴状区与沟流区上的传热之和,建立了反映界面效应影响的过渡状冷凝传热模型.设计了人工形成沟流形态的冷凝表面,其实验结果与模型计算结果吻合;模型计算也与实际自然形成沟流冷凝形态的传热过程吻合.模型对滴状区的传热计算,以液滴分布时间序列构象模型为基础,并将滴状区最大液滴与沟流级别相关联,得到与界面效应相关的滴状区传热模型;沟流区传热计算,以在一定厚度液膜上的冷凝传热模型为基础,并根据沟流形态模型,求出液膜厚度与沟流区所占面积分率.模型描述了过渡状冷凝形态形成特征以及过渡状冷凝传热系数随表面自由能差渐进变化的规律.     

Use of sodium and potassium butyl xanthate as accelerator for room temperature prevulcanization of natural rubber latex

Sodium and potassium butyl xanthates (Nabxt and Kbxt) were prepared in the laboratory. Characterization of these xanthates were done using Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (¹H NMR) spectroscopy, thermogravimetric analysis (TGA), and differential thermal analysis (DTA) techniques. These xanthates were used as accelerators for the prevulcanization of natural rubber latex (NRL) at room temperature. Optimization of prevulcanization time was done. Films were casted from these prevulcanized NRL. Tensile properties of latex vulcanisates were measured and potassium butyl xanthate gave superior properties to the NRL films compared with sodium butyl xanthate. Effect of thermal ageing on tensile properties of these prevulcanized NRL films was also investigated and these properties were found to be improved after thermal ageing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

温度对杨木木粉表面自由能和表面极性的影响

通过毛细管上升法测定了经过不同温度处理的杨木木粉的表面接触角,依据Washburn方程和Owens-wendt-Kaelble法,求解了经过不同温度处理的杨木木粉的表面自由能及其极性分量和非极性分量。结果表明,杨木木粉的表面自由能为23.43 mN/m,体现分子色散力的非极性分量为4.64 mN/m,在处理时间为2 h的条件下,随着处理温度的上升,杨木木粉的总表面自由能略有下降,体现其分子色散力的非极性表面自由能上升,体现其表面极性值的极性表面自由能下降,并分析了上述结果的原因。     

Effect of crosslinking on the surface free energy and surface reorganization of waterborne fluorinated polyurethane

To endow waterborne fluorinated polyurethanes (WFPUs), films with stable lower surface free energy and lower surface reorganization after the films contacted with water, a series of crosslinked WFPUs (CWFPUs) emulsions were prepared by adjusting the content of aziridine (AZ). The effect of crosslinking on the surface free energy, glass-transition temperature (T _g), water absorption, and surface composition of dry/hydrated WFPUs and CWFPUs films were studied by CAs test, dynamic mechanical analysis, water absorption measurements, and X-ray photoelectron spectroscopy. When the fluorine content was 0.5%, the surface free energy of the CWFPUs films modified by 0.4% AZ content (CWFPU-6-0.5-CK0.4) reached to the lowest value of 15.76 mN m⁻¹ which almost equaled to the surface free energy (15.45 mN m⁻¹) of the dry uncrosslinked films (WFPU-6-0.5). With the increasing of AZ content, the T _{g, hard} of hard segments of the CWFPUs films increased and the water absorption of the CWFPUs films decreased, which suggested the formation of the crosslinked network structures. The studies of the surface elements and groups composition of dry/hydrated WFPUs and CWFPUs both confirmed that the surface reorganization and the migration of fluorinated side chains were restricted by the crosslinked network structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47167.     

Synthesis and performance enhancement of novel polybenzoxazines with low surface free energy

A new siloxane‐imide‐containing benzoxazine, BZ‐A6, has been successfully synthesized. The thermal properties of the polybenzoxazine (PBZ) prepared from BZ‐A6 (PBZ‐A6) are superior to those of conventional PBZs lacking siloxane groups. The normally brittle PBZs are toughened significantly as a result of adding siloxane‐imide moieties. Moreover, the thermal and UV stabilities of the surface free energy of PBZ‐A6 are dramatically improved over the conventional bisphenol‐A‐type PBZ. Siloxane‐imide PBZs are more suitable for application as low‐surface‐free‐energy materials that are highly resistant to temperature and UV radiation. PBZ‐A6 may also be useful in weather‐resistant and self‐cleaning coating materials because of its low surface free energy and good thermal and UV resistance. Copyright © 2011 Society of Chemical Industry     

Solid surface free energy components determination by the thin-layer wicking technique

A thin-layer wicking technique [1] and van Oss et al.'s [2] approach to interfacial free energy interactions were tested to determine the solid surface free energy components: apolar Lifshitz-van der Waals, y^l,w _y; and polar, electron donor, γ^- _y, and electron acceptor, γ⁺ _y. For this purpose, the penetration rates of n-alkanes, diiodomethane, water, formamide, toluene and chloroform were measured. For these studies, silica, used for thin-layer chromatography, and α-Al₂O₃ were used as the model solids. It was found that both are strongly polar, electron donor solids with weak electron acceptor interactions. It is concluded that van Oss, Good et al.'S [2] approach to the interfacial free energy interactions and the thin-layer wicking technique are very useful for cxplaining many interfacial phenomena taking place in the dispersed systems. However, more experimental work using different systems is needed.     

The role of the surface free energy in the selection of a suitable excipient in the course of a wet-granulation method

Pellets containing metronidazole were produced in a centrifugal granulator, with hydroxypropylcellulose (Klucel LF®) as binding agent, and corn starch, microcrystalline cellulose (Vivapur 101®) and lactose as excipients. The wettability of the pharmaceutical powders was assessed by means of contact angle measurements, and the dispersive and polar surface energies were determined. The spreading coefficients, the work of adhesion and the work of cohesion were calculated and correlated with the pellet properties (friability, bulk and tapped density, and porosity). The aim was to investigate the role of the surface free energy of one- and two-component powder compositions in pellet production. The interactions between the particles were found to be connected with the measured pellet parameters. It was concluded that, in the course of the growth of the pellets, the particle sizes of the pharmaceutical powders and the interactions between them are important. If the work of cohesion of the binder is lower than the work of cohesion of the substrate and the work of adhesion, then the optimal amount of the binding agent is that which coats the particles uniformly in minimal quantity and in continuous layer.     

Wettability and surface free energy of bovine serum albumin films

Measurements of the contact angle for water, glycerol, formamide, ethylene glycol, and diiodomethane on polymethyl methacrylate covered by adsorptive bovine serum albumin (BSA) films were made. Adsorption was performed from solutions in the concentration range 0–100 g/L. From the obtained contact angles the Lifshitz-van der Waals components and the values of the electron-acceptor and electrondonor parameters of the acid-based components of the films were calculated for six triplets of liquids. The biggest changes in the BSA film structure occurred under a monolayer coverage (i.e., at BSA concentrations of <2.5 g/L). On the basis of the contact angles of glycerol, ethylene glycol, and formamide it was concluded that the density of BSA polar groups was almost constant. The surface density of the hydrophobic part of the BSA film also seemed constant regardless of the concentration of the solution from which the BSA adsorptive film was created. This conclusion could be drawn from the almost constant contact angle of diiodomethane.