Microstructure and properties of polyhydroxybutyrate-calcium phosphate cement composites

The biopolymer (polyhydroxybutyrate) microparticles-calcium phosphate composites were prepared by mechanical mixing of the basic composite components with the addition of hardening liquid after ethanol-composite mixture suspension moulding. The composite microstructures were more compact than the pure cement samples as confirmed by the lower values of specific areas and mesopore volumes. Both the specific areas and mesopore volumes decreased with soaking time in a simulated body fluid. The low polyhydroxybutyrate degradation in composites was found after soaking in simulated body fluid, which was terminated after one week. The formation of a dense apatite layer bonded directly to the surface of polyhydroxybutyrate microparticles was observed. The highest diametral tensile strength (13 MPa) and compressive strength (95 MPa) values of up to 50 % higher than in pure cement were measured in samples with 10 % of polyhydroxybutyrate. The addition of polyhydroxybutyrate microparticles had no effect on the setting time.     

Membrane permeation-controlled transdermal delivery system design. Influence of controlling membrane and adhesive on skin permeation of isosorbide dinitrate

A membrane permeation-controlled transdermal delivery system (MC-TDS) of isosorbide dinitrate (ISDN), a model drug, was prepared from polyvinyl alcohol aqueous gel containing the drug, a membrane consisting of ethylene-vinyl acetate copolymer membrane and acrylic adhesive (EV-a). The permeability of ISDN through the EV-a membrane was 2.5 times higher than that through excised hairless rat skin. The ratio of plasma concentration of ISDN after application of MC-TDS on stripped (damaged) skin relative to intact skin was lower than that after application of Frandol tape-S, a marketed ISDN TDS, which suggests that the EV-a membrane might work as a control membrane for overall delivery rate of ISDN to the body. When MC-TDS stored at 30 degrees C for 13.5-48h was applied to the damaged skin, however, the initial plasma concentration of ISDN was very much higher than the expected therapeutic level and was not controlled by the EV-a membrane. The initial high plasma concentration of ISDN after application of the stored MC-TDS on the damaged skin was due to migration of ISDN from the reservoir to the adhesive during storage at 30 degrees C. The migration of drugs into the adhesive might be an important problem in developing efficient MC-TDS.     

Interfacial toughness in polymer‐layered laminar composites

The investigation of the interfacial toughness of polymer layered laminar composites with two different approaches produced results differing by up to an order of magnitude and following opposite trends with respect to the strain rates. The flexural modulus and neutral axis of a constrained epoxy‐adhesive layer bound to a painted metal substrate varied with the thickness of the adhesive layer. The adhesion energy depended on the rate at which the force was transmitted to the adhesion bonds—not just on the strength of the adhesion bonds—and on the concomitant strain hardening at high strain rates. As the strain rate and thickness of the polymer layer increased, the transition from a cohesive mode to an adhesive–cohesive (polymer–polymer interface) mode of debonding led to the observed high adhesion energy. The high adhesion energy and increased strain hardening were attributed to the formation of organic–inorganic composites and nanocomposites within the polymer matrix, which evolved as a result of the interactions between the metal oxide pigments and fillers with the polymer matrix during curing. Scission of the polymer chains at the interface was proposed to be the predominant fracture mechanism; it was based on the high relaxation time (～10¹⁷ s) and the high activation energy (～175 kJ mol^?1). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3822–3835, 2004     

层层组装构筑聚电解质/碳纳米管导电黏附膜

首先将聚烯丙基胺盐酸盐与碳纳米管制成复合物(PAH-CNT), 再通过层层组装技术构筑了聚丙烯酸和碳纳米管混合物(PAA-CNT)与PAH-CNT多层复合膜(PAH-CNT/PAA-CNT). PAH-CNT/PAA-CNT多层复合膜同时具有导电和黏附性能. 在玻璃和ITO基片上沉积的PAH-CNT/PAA-CNT多层复合膜的最大拉伸剪切强度接近7 MPa, 即1 cm²的黏附膜可以承受约70 kg的重物. 碳纳米管的引入使PAH-CNT/PAA-CNT多层复合膜具有更好的导电性.     

Adhesion enhancement through micropatterning at polydimethylsiloxane-acrylic adhesive interfaces

Adhesion at polydimethylsiloxane (PDMS)-acrylic adhesive interfaces is shown to be enhanced through micropatterning of the PDMS substrate. By varying the geometry of the patterns (groves and hexagonal arrays of pillars of micrometer sizes, obtained through soft lithography techniques) and comparing rigid and deformable substrates, the respective roles of the geometry and the size and flexibility of the pattern features on the level of adhesion have been analyzed. For cylindrical pillars, two regimes are clearly identified: for a relatively low aspect ratio (h/r < 3, with h and r, respectively, the height and the radius of the pillars), soft patterned substrates are more efficient than rigid ones at increasing adhesion, pointing out the role of the elastic energy associated with the deformation of the pattern that is lost when the adhesive detaches from the substrate. Using scaling laws, the predominant contribution to that elastic energy can be further identified: deformation of the substrate underlying the pillars for h/r < 1.6 or bending of the pillars for h/r > 1.6.; for a high aspect ratio (h/r > 3), only rigid patterned substrates enhance adhesion, then the only possible contribution to energy dissipation comes from the enhanced viscoelastic losses associated with the pattern that induce modifications of the strain field within the adhesive layer. Soft, high aspect ratio patterns lose their efficiency even if still bent under the effect of the peel forces. This is because when bent, some of the pillars touch each other and remain stuck together, lying flat on the surface after the passage of the peel front. The bending elastic energy of the pillars (which is still lost) is then balanced by the corresponding gain in surface energy of the substrate in the peeled region. These systematic experiments demonstrate that the ability of the patterned surface to be deformed plays a crucial role in enhancing adhesion and allow us to propose a way to fine tune the level of adhesion at PDMS-acrylic adhesive interfaces, independently of the chemistry of the adhesive.     

催化氧化木薯淀粉的结构与胶粘性能

考察了催化剂硫酸亚铁对氧化木薯淀粉的绝对分子量及其分布、羧基和羰基含量以及其胶粘性能的影响。结果表明,催化氧化使木薯淀粉的氧化降解时间减少到0.5 h,羧基和羰基含量分别增加了105%和12%以上。用高效凝胶渗透色谱与多角度激光光散射仪联用技术分析氧化淀粉的结果表明,催化氧化淀粉的绝对分子量比无催化氧化淀粉的小,且分布均匀。由催化氧化淀粉制得的淀粉胶粘剂的固含量达28.9%,干燥15 m in时粘接强度达57 N。     

Polymer alloy adhesive film made up of epoxy resin and aromatic polyester

Printed wiring boards (PWBs) with high wiring density such as thin multilayer PWBs and flexible PWBs requiring bonding sheets with superior thermal and adhesive properties, and must have a flat board surface. To meet these requirements, a polymer alloy adhesive film made up of epoxy resins and aromatic polyester has been developed. The crosslinking reaction between the components was utilized to improve thermal properties. The polymer alloy adhesive film demonstrates good heat resistance and adhesiveness. It features a low processing pressure of 2 MPa at 170°C and gives the board surface greater flatness, which is better for the fine wiring of PWBs.     

一种新型可降解蓝光固化医用粘合剂的合成及其性能研究

临床外科手术缝合费时费力,且容易留下疤痕,医用粘合剂为解决这些问题提供了一种有效手段。本文基于在生物材料领域广泛应用的可降解材料聚癸二酸甘油酯（PGS）,研制了一种新型的可降解蓝光固化医用粘合剂。以PGS为基体与甲基丙烯酸（2-异氰基乙基）酯反应制得聚癸二酸甘油酯接枝甲基丙烯酸（2-异氰基乙基）酯（PGS-IM）粘结剂,其结构和性能经¹H NMR, ATR-FTIR, TGA和DSC表征。并测试了其蓝光固化后的粘结性能,考察了其生物相容性。结果显示：PGS-IM的玻璃化转变温度为-30.6 ℃;玻璃和PET板的粘结强度分别为0.84±0.12 MPa和0.39±0.07 MPa。 RAECs培养实验显示其具有良好的生物相容性。     

Gelation and adhesion behavior of mussel adhesive protein mimetic polymer

An acrylamide‐type copolymer containing catechol, amino, and hydroxyl groups was synthesized as a mimetic of the natural mussel adhesive protein (MAP). The obtained copolymer in a phosphate buffer solution (pH = 8.0) formed a hydrogel within 2 h under air, whereas gelation did not proceed under argon atmosphere. We confirmed that the cross‐linking reaction of the synthesized MAP mimetic copolymer was triggered by aerobic oxidation of catechol moieties to form an adhesive hydrogel. Two aluminum plates were adhered by the gelation of the MAP mimetic copolymer solution under humid air at room temperature. The interfacial region between the two aluminum plates failed at a lap shear strength of 0.46 MPa due to cohesive failure of the hydrogel. The adhesion strength was dominated by mechanical strength of the hydrogel as well as the interface interaction of catechol groups with substrate surface. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

基于肟-氨基甲酸酯的超强自修复水性聚氨酯胶粘剂的制备及性能分析

基于肟-氨基甲酸酯热可逆成键原理, 利用可工业批量获得的二甲基乙二肟为构建单元, 设计合成了一类具有高强动态网络结构的水性乳液, 制备出综合性能与重复利用兼顾的聚氨酯胶粘剂; 通过变温红外光谱结合差式扫描量热仪分析了肟-氨基甲酸酯升温过程的可逆成键特性, 并利用动态力学谱仪对变温过程的网络松弛行为进行了研究. 结果表明, 合理的硬段含量与结构设计赋予了胶粘剂极高的粘结强度(25 MPa, 一般商业通用热熔胶的粘结强度< 6 MPa)、 优异的乳液稳定性(粒径<100 nm)以及接近97%的修复效率(160 ℃, 10 min下的剪切搭接实验). 该类乳液具有超强、 稳定及工艺可放大等特性, 为水性自修复胶粘剂的商业化开发提供了新途径和新思路.     

Correlation between glycated lipoproteins and fructosamine level in serum.

The correlation between the level of fructosamine and glycated proteins, including glycated lipoproteins, in serum from diabetic and nondiabetic subjects was studied. Assay of glycated proteins in serum was performed using an agarose gel film electrophoresis with nitroblue tetrazolium coloration. Glycated albumin correlated well with the fructosamine level in the diabetics (r = 0.83-0.92, p less than 0.01) but showed no correlation with the nondiabetics (r = 0.25-0.26). Also, a high correlation between the glycated beta-lipoprotein and fructosamine levels was observed in diabetic patients with hyperglycemia and in nondiabetic subjects with a high risk of atherogenesis (atherogenic index, low-density lipoprotein-cholesterol/high-density lipoprotein-cholesterol greater than 2.8) (r = 0.51-0.66, p less than 0.01). Nondiabetics with a high level of beta-lipoprotein, which is well known to cause high atherogenesity, showed a high level of glycated beta-lipoprotein similar to that in the diabetic groups with hyperglycemia; therefore, the high level of glycated beta-lipoprotein seems to be attributable not only to the hyperglycemia-accelerated glycation of beta-lipoprotein but also to an increase in the level of beta-lipoprotein in serum. Consequently, the present results show that the fructosamine level in serum reflects not only the glycation of albumin but also that of lipoproteins which are known to increase in diabetes mellitus.     

Bioinspired Design Provides High‐Strength Benzoxazine Structural Adhesives

A synthetic strategy to incorporate catechol functional groups into benzoxazine thermoset monomers was developed, leading to a family of bioinspired small‐molecule resins and main‐chain polybenzoxazines derived from biologically available phenols. Lap‐shear adhesive testing revealed a polybenzoxazine derivative with greater than 5 times improved shear strength on aluminum substrates compared to a widely studied commercial benzoxazine resin. Derivative synthesis identified the catechol moiety as an important design feature in the adhesive performance and curing behavior of this bioinspired thermoset. Favorable mechanical properties comparable to commercial resin were maintained, and glass transition temperature and char yield under nitrogen were improved. Blending of monomers with bioinspired main‐chain polybenzoxazine derivatives provided formulations with enhanced shear adhesive strengths up to 16 MPa, while alloying with commercial core–shell particle‐toughened epoxy resins led to shear strengths exceeding 20 MPa. These results highlight the utility of bioinspired design and the use of biomolecules in the preparation of high‐performance thermoset resins and adhesives with potential utility in transportation and aerospace industries and applications in advanced composites synthesis.     

The influence of polysulfones of various structures on the properties of adhesive materials

A study of a samples of polyarylsulfones and polyarylsulfidesulfones with a glass-transition point of 210–245°C as received and in the formulations of adhesive compositions has been conducted. It has been shown that the developed adhesive compositions containing polyarylsulfones are capable of forming a film and provide high strength indices of adhesive joints in shear of 23–29 MPa within a temperature range from 20 to 150°C.     

Rapid,On‐Command Debonding of Stimuli‐Responsive Cross‐Linked Adhesives by Continuous,Sequential Quinone Methide Elimination Reactions

Adhesives that selectively debond from a surface by stimuli‐induced head‐to‐tail continuous depolymerization of poly(benzyl ether) macro‐cross‐linkers within a poly(norbornene) matrix are described. Continuous head‐to‐tail depolymerization provides faster rates of response than can be achieved using a small‐molecule cross‐linker, as well as responses to lower stimulus concentrations. Shear‐stress values for glass held together by the adhesive reach 0.51±0.10 MPa, whereas signal‐induced depolymerization via quinone methide intermediates reduces the shear stress values to 0.05±0.02 MPa. Changing the length of the macro‐cross‐linkers alters the time required for debonding, and thus enables the programmed sequential release of specific layers in a glass composite material.     

Rapid,On‐Command Debonding of Stimuli‐Responsive Cross‐Linked Adhesives by Continuous,Sequential Quinone Methide Elimination Reactions

Adhesives that selectively debond from a surface by stimuli‐induced head‐to‐tail continuous depolymerization of poly(benzyl ether) macro‐cross‐linkers within a poly(norbornene) matrix are described. Continuous head‐to‐tail depolymerization provides faster rates of response than can be achieved using a small‐molecule cross‐linker, as well as responses to lower stimulus concentrations. Shear‐stress values for glass held together by the adhesive reach 0.51±0.10 MPa, whereas signal‐induced depolymerization via quinone methide intermediates reduces the shear stress values to 0.05±0.02 MPa. Changing the length of the macro‐cross‐linkers alters the time required for debonding, and thus enables the programmed sequential release of specific layers in a glass composite material.     

Study of the epoxyline resin ED-20 hardening by modified oligoaminoamide dimerizated fatty-acid derivates

Resin ED-20 hardening by an oligoaminoamide hardener is analyzed by the differential scanning calorimetry (DSC) method. The optimal resin-to-hardener proportion is determined. Physical, mechanical, and thermal characteristics of the hardened polymers are determined. The high adhesive ability of the oligoaminoamide mixture towards steel is analyzed.     

高变质程度无烟煤热天平二氧化碳加压催化气化动力学——热天平等温热重法

以碳酸钠为催化剂，在加压下用热天平等温热重法研究了四种高变质程度无烟煤（挥发分Vad=2.69%~4.35%）二氧化碳催化气化反应动力学，考察了0.101MPa~3MPa对二氧化碳催化气化反应的影响。结果表明，压力大于2.0MPa，增大压力不再加快反应速率。在2.0MPa、750℃~950℃测定实验无烟煤的转化率与时间的关系，用缩芯模型进行较好地拟合。按反应速率常数判定煤样活性大小顺序为：永安丰筛煤>永安加筛煤>永定煤>上京煤，活化能为： 157.21kJ/mol~185.89kJ/mol，要比相同煤种常压二氧化碳催化气化时具有更大的反应速率常数、 活化能和指前因子。 850℃及较低压力 0.101MPa~2.0MPa下，给出永安加筛煤气化动力学方程中的压力修正指数为0.34744，与文献报道一致。     

柔性主链的支化结构对冲击硬化材料性能的影响

以羟基封端的二甲基甲基乙烯基(硅氧烷与聚硅氧烷)(C=C—PDMS—OH)为接枝主链 ,将单氢化端基二甲基硅氧烷(H-PDMS)作为接枝支链,通过卡斯特催化剂催化二者间的硅氢化反应形成具有瓶刷结构的柔性主链(Brush PDMS-OH)。 再通过三甲氧基硼氧六环(TMOB)的动态交联和异佛尔酮二异氰酸酯扩链剂(IPDI)的稳态化学交联,制备主链带有支化链的冲击硬化材料(Brush Impact Hardening Polymer,B-IHP)。 通过核磁共振波谱仪(NMR)、傅里叶变换红外光谱仪(FTIR)和流变仪等测试手段对材料结构和性能进行表征。 结果表明,B-IHP具有良好的机械性能和冲击硬化性能,拉伸强度达到9.8 MPa,冲击硬化值达到3500以上。 B-IHP具有良好的自愈合性能,愈合效率可达95%以上,愈合时间仅为6 h。 该柔性主链的支化结构可以明显降低主链发生链缠结的相对分子质量阈值,提升材料的冲击硬化性能和自愈合能力。     

A Soft Shape Memory Reversible Dry Adhesive

Transfer printing is a critical procedure for manufacturing stretchable electronics.During such a procedure,stamps are utilized to transfer micro devices from silicon wafers to stretchable polymeric substrates.In addition to conventional silicone rubber stamps,epoxy resin based shape memory stamps have been developed and the transfer yield is thus significantly promoted.However,elastic modulus of the epoxy stamps is too high at both glassy and rubbery states,which may break the brittle micro devices during the adhesion process under mechanical pressure.In this work,we synthesized a copolymer of butyl acrylate (BA) and polycaprolactone diacrylate (PCLDA) as a soft reversible dry adhesive enabling a shape memory capability based on crystalline transition of polycaprolactone (PCL) segments.For the sample containing 40 wt％ BA and 60 wt％ PCLDA,Young's modulus was 8.3 and 0.9 MPa respectively below and above the thermal transition temperature,which was much lower than that of the epoxy adhesive.On the other hand,the soft material still provided nearly ideal shape memory fixity and recovery ratios.Subsequently,shape memory surface with cone-shaped microstructure was prepared,which enabled a heating induced strong-to-weak adhesion transition when the microstructure recovered from a pressed temporary morphology to the permanent cone-shaped morphology.Such a soft reversible dry adhesive may contribute to large-scale and automated transfer printing processing.     

Adhesive effect of low-density polyethylene gels on polyethylene moldings

Adhesive effect of low density polyethylene (LDPE) gels in organic solvents such as decalin, tetralin, ando-dichlorobenzene on high density polyethylene (HDPE) moldings has been investigated by shearing tests, electron microscopy, and DSC measurements. When heated at 110°C for 2 h, all of the gels showed strong adhesive strengths around 30 kg/cm², which is sufficiently strong for practical uses. It has been found that the adhesive strength increases with the heating temperature and that the temperature at which the heated gel begins to exhibit the adhesive effect depends upon solvents and is about 30° lower than that of the HDPE gels.