Adhesion at Poly(Butylacrylate)–Poly(Dimethylsiloxane) Interfaces

We present an investigation of the adhesion modulation mechanisms of silica-like nanoparticles (MQ resins) incorporated in polydimethylsiloxane (PDMS) elastomers and acrylic adhesives. The Johnson-Kendall-Roberts (JKR) test has been used to gain information on the both zero velocity and the velocity dependence of the adhesive strength, avoiding as much as possible contributions to the adhesive strength of bulk dissipation in the adhesive (which is not the case with peel tests). As the incorporation of the MQ resins into the elastomers deeply affects their own mechanical properties, the loading and unloading curves of small poly(butylacrylate) (PBA) lenses on either PDMS elastomers, adsorbed PDMS and pure MQ resin layers are compared in a systematic manner. The PBA chains are observed to have a neat affinity for the MQ resin nanoparticles. When MQ resins are present at the interface, they tend to prevent facture propagation, thus producing a larger deformation of the PBA lens. The modulation of adhesion is then dominated by the corresponding dissipation inside the acrylic adhesive.     

Modulation of Adhesion at Silicone Elastomer-Acrylic Adhesive Interface

To characterize the role of small silica like nanoparticles (MQ resins) in the modulation of adhesion at polydimethyl siloxane (PDMS) elastomers-acrylic adhesive contacts, we have designed systems in which the roles of MQ resins in enhancing interactions at the interface and in increasing viscoelastic dissipations in the elastomer layer could be separated. First, the contact between elastomers with various MQ resin contents and PDMS layers made of densely grafted short chains has been investigated through Johnson-kendall-Roberts (JKR) tests, in order to characterize how the dissipations in the elastomer depend on the resin content. The same elastomers in contact with thin-surface-anchored acrylic layers were then tested through JKR tests to determine the role of enhanced interactions in the modulation of adhesion at the interface due to the resins. In these experiments, the thickness of the acrylic layer was kept small enough so that dissipations in the acrylic adhesive could be neglected. Both G₀, the adhesive strength at zero fracture velocity, and G( V), the velocity-dependent fracture toughness, strongly depend on the MQ resin content and on the contact time, suggesting the progressive building of strong interactions between acrylic and elastomer chains.     

Modulation of Adhesion at Silicone Elastomer–Acrylic Adhesive Interface

To characterize the role of small silica like nanoparticles (MQ resins) in the modulation of adhesion at polydimethyl siloxane (PDMS) elastomers–acrylic adhesive contacts, we have designed systems in which the roles of MQ resins in enhancing interactions at the interface and in increasing viscoelastic dissipations in the elastomer layer could be separated. First, the contact between elastomers with various MQ resin contents and PDMS layers made of densely grafted short chains has been investigated through Johnson–kendall–Roberts (JKR) tests, in order to characterize how the dissipations in the elastomer depend on the resin content. The same elastomers in contact with thin-surface-anchored acrylic layers were then tested through JKR tests to determine the role of enhanced interactions in the modulation of adhesion at the interface due to the resins. In these experiments, the thickness of the acrylic layer was kept small enough so that dissipations in the acrylic adhesive could be neglected. Both G ₀, the adhesive strength at zero fracture velocity, and G ( V), the velocity-dependent fracture toughness, strongly depend on the MQ resin content and on the contact time, suggesting the progressive building of strong interactions between acrylic and elastomer chains.     

Modulation of Adhesion at Acrylic Adhesive-Silicone Elastomer Interfaces

We have recently reported a systematic investigation of the role of MQ resins (small silica-like nanoparticles) in the modulation of adhesion at silicone elastomer lens—nanometric thin acrylic surface anchored layer deposited on a silicon wafer through loading and unloading JKR experiments. This particular system was chosen as it allowed one to vary the MQ resin content in the elastomer, and to test its resulting effect on both the thermodynamic work of adhesion and the adhesive strength at elastomer—acrylic layer interfaces, avoiding any complication due to bulk mechanical properties of a relatively thick (in the micron range) acrylic layer. We present here a complementary investigation, aimed at understanding the role of the resins in the development of specific interactions at the interface. To do so the adhesive energy between silicone elastomers containing various amounts of MQ resins and model substrates made of self-assemble monolayers of thiol molecules with various amounts of carboxylic terminations have been measured through JKR tests. We show that the level adhesion at these interfaces results from a competition between increased interactions and decreased mobility associated with the incorporation of the resins inside the elastomer.     

Modulation of Adhesion at Acrylic Adhesive-Silicone Elastomer Interfaces

We have recently reported a systematic investigation of the role of MQ resins (small silica-like nanoparticles) in the modulation of adhesion at silicone elastomer lens—nanometric thin acrylic surface anchored layer deposited on a silicon wafer through loading and unloading JKR experiments. This particular system was chosen as it allowed one to vary the MQ resin content in the elastomer, and to test its resulting effect on both the thermodynamic work of adhesion and the adhesive strength at elastomer—acrylic layer interfaces, avoiding any complication due to bulk mechanical properties of a relatively thick (in the micron range) acrylic layer. We present here a complementary investigation, aimed at understanding the role of the resins in the development of specific interactions at the interface. To do so the adhesive energy between silicone elastomers containing various amounts of MQ resins and model substrates made of self-assemble monolayers of thiol molecules with various amounts of carboxylic terminations have been measured through JKR tests. We show that the level adhesion at these interfaces results from a competition between increased interactions and decreased mobility associated with the incorporation of the resins inside the elastomer.     

高温硫化硅橡胶胶粘剂的研究

制备了一种有机硅胶粘剂,该胶粘剂主要由苯基硅橡胶与ＭＱ硅树脂组成,对影响该胶粘剂胶接强度的因素进行了研究。结果表明：该胶粘剂对铝有较好的胶接强度,其剪切强度与ＭＱ树脂的结构有很大关系,随ＭＱ树脂用量的增加而提高,催化剂的种类和用量对胶接强度也有影响。另外,该胶粘剂具有优良的耐高温老化性能以及对聚四氟乙烯较好的胶接性能。     

PU/PA纳米粒子改性酚醛树脂胶粘剂的研究

采用自乳化法制备PU/PA纳米粒子,并对酚醛树脂进行增韧改性.考查了丙烯酸酯单体种类、用量以及环氧树脂用量对改性酚醛树脂粘接性能的影响.借助TG、DSC、SEM和TEM对改性酚醛树脂体系的耐热性能、固化反应和微观形态进行了表征.结果表明,PU/PA纳米粒子的加入使酚醛树脂的常温和高温粘接强度显著增加,提高了酚醛树脂的固...     

Synthesis and characterization of MQ silicone resins

MQ silicone resins, which represent a broad range of hydrolytic condensation products of monofunctional silane (M) and tetrafunctional silane (Q), were synthesized by reaction of water glass with hexamethyldisiloxane. The optimum reaction time and the optimal reaction temperature is 30 min and 30–40°C, respectively. Concentrated hydrochloric acid is the best one among those catalysts tested. In large-scale experiments (420–1680 mL), the favorable feeding order is catalyst first, and then water glass, the mixture of hexamethyldisiloxane and ethanol last and most MQ silicone resin was observed. The structure of MQ silicone resin was characterized by FT-IR and GPC spectra. The MQ silicone resin shows narrow molecular weight distribution and the number average molecular weight of MQ silicone resin is 2917. The silicone pressure sensitive adhesive prepared from as-synthesized MQ resin has good tack (29#) and 180° peel adhesion (5.630N/20 mm). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Two‐component acrylic structural adhesive initiated by tributylborane for untreated PET adhesion

In order to improve the adhesion strength of acrylic adhesive to untreated poly(ethylene terephthalate) (PET) substrate, two‐component acrylic structural adhesives initiated by tributylborane were prepared. The effects of acrylic monomers, elastomers, decomplexers, and oligomers on the adhesion properties of two‐component acrylic structural adhesive were investigated in sequence. It is found that the shear strength on PET of adhesives toughened by acrylonitrile–butadiene–styrene copolymer and carboxyl‐terminated butadiene–acrylonitrile copolymer is higher than that of commercial adhesives Dp8010NS and Loctite 3030. A tailored oligomer was synthesized from hydroxyl propyl–terminated polydimethylsiloxane and 3‐isopropenyl‐α,α‐dimethylbenzyl isocyanate. It is also noticed that premature failure usually takes place in the lap shear test samples due to the brittleness of the acrylic adhesive, except in the sample of adhesive modified by tailored oligomer. Excellent adhesion to the PET substrate is achieved by this adhesive modified by tailored oligomer, with a lap shear strength above 11 MPa and T‐peel strength up to 5.34 N/mm. Additionally, the resulting adhesive is qualified for the structural bonding of PET materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46612.     

自交联型丙烯酸酯树脂纸塑复合胶的制备与性能

以丙烯酸丁酯(BA)、酪酸乙烯酯(VAC)为主要原料,适当引入丙烯酸(AA)、丙烯酸羟丙酯(HPA)等活性功能单体,在半连续加料方式下通过种子乳液聚合法制备乳液型纸塑复合胶。探讨了单体选择及配比和功能单体、引发剂与乳化剂用量对乳胶性能的影响。最后对松香增粘作用进行了试验研究。     

新型硅改性丙烯酸酯压敏胶的研究

MQ硅树脂可用作改性聚丙烯酸酯类压敏胶,在保持较好力学性能(初粘性、持粘性和剥离强度)和绝缘性的同时,可较大地提高硅改性压敏胶的耐高温性能。MQ树脂的结构和压敏胶的性能用29Si-NMR,DSC,粘性等表征。MQ硅树脂含量对硅改性压敏胶性能影响极大,通常MQ硅树脂用量为(0.3～0.5)%时具有较好的综合性能。该压敏胶粘剂可以直接涂布于经电晕处理的聚酯膜制备压敏胶粘带,便于工业化生产。     

Structure and properties of epoxy resins modified with acrylic particles

The morphology and material properties of dicyandiamide (DICY)‐cured epoxy resins modified with acrylic particles consisting of a PBA (polybutyl acrylate) core and a PMMA (polymethyl methacrylate) shell and epoxy resins modified with acrylic rubber (PBA) particles alone were studied. It was found that the epoxy system modified with core/shell acrylic particles showed higher fracture toughness, indicating that the modification had a larger effect on improving the material properties of the epoxy resin. A characteristic shown by the core/shell acrylic particles is that they swell along with the epoxy resin under exposure to heat and gel before the latter cures. In this process, the epoxy resin penetrates the surface of the shell layer and a bond is formed between the epoxy matrix and the core/shell acrylic particles. This suggests that the epoxy matrix around the core/shell acrylic particles has the effect of increasing the level of energy absorption due to plastic deformation of the matrix. This is thought to explain why the epoxy resin modified with core/shell acrylic particles showed higher fracture toughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2955–2962, 1999     

Preparation and properties of UV-curable poly(dimethylsiloxane) urethane acrylate. II. Property-structure/molecular weight relationships

A series of UV-curable polyurethane acrylate resins based on hydroxy-terminated polydimethylsiloxane (PDMS) soft segments with different molecular weights and various diisocyanate hard segments were synthesized. The products were obtained by employing direct-addition polymerization techniques in a nonsolvent system. The structures of the final products were elucidated by IR and ¹H-NMR. The fundamental and physical properties of this type of UV-curable material, the effects on properties by varying the molecular weight of PDMS or the type of diisocyanates, and the effect of using various reactive diluents were widely studied. This resin possessed good optical, electrical insulating, and adhesive properties. The mechanical strength of UV-cured films corresponds approximately to the ratio of hard segments within these material and the dielectric insulating properties correspond to the chain length of PDMS.     

Effect of model fillers on the adhesive strength of pressure-sensitive tapes

—The effect of various model fillers, namely glass beads, 'Spheriglass', and PTFE powder, on the adhesive strength of natural rubber (NR) and poly(n-butyl acrylate) (PBA) tapes has been investigated. Glass fillers treated with alkyl chlorosilane were also used. The adhesive strength was measured over a range of rates and temperatures, and corrections for the thickness of the adhesive and volume fraction of the polymer were introduced into the rate term. It was observed that the adhesive strength of PBA tapes filled with 20% PTFE is comparable to that of the control sample without filler. The strength measured over a range of strain rates increased for both untreated and treated Spheriglass-filled adhesives. Filled NR adhesives showed an enhanced strength only at very high strain rates. With 40% PTFE, this increase was quite apparent. The mechanism of improvement of the strength of adhesion due to the incorporation of a filler is explained. The addition of a filler introduces an additional mechanism of energy dissipation during deformation of the adhesive and a higher energy will be expended due to debonding of the filler and hysteresis.     

Polyether and polyester polyol based glycidyl-terminated polyurethane modified epoxy resins: Mechanical properties and morphology

A glycidyl-terminated polyurethane prepolymer was synthesized and used to enhance the properties of epoxy resins. Some properties of glycidyl-terminated PU/epoxy with polyether based (PPG) and polyester based (PBA) glycidyl-terminated PU were investigated in this research. The polyether based glycidyl-terminated PU(PPG) modified epoxy resin proved to be superior to conventional epoxy resins in improved impact strength and fracture energy, but not tensile strength, tensile modulus, flexural strength and flexural modulus. On the other hand, the polyester based glycidyl-terminated PU(PBA) modified epoxy resin had increased mechanical properties while showing slight variation of impact strength and fracture energy. Different mechanisms for this behaviour are advanced in this paper.     

甲基MQ及MTQ型硅酮树脂的合成及其特性

研究了以偏硅酸钠、六甲基二硅氧烷为基本原料合成甲基ＭＱ及ＭＴＱ型硅酮树脂的方法,内容包括水解反应温度的影响,投料比例的影响,反应时间的影响,交链剂对ＭＴＱ型树脂性能的影响以及ＭＱ及ＭＴＱ树脂与液体硅橡胶配伍作为胶粘剂的粘接性能的研究等。     

The effect of nanoalumina silanisation in tetraglycidylether epoxy adhesive

The efficiency of different surface modifications on alumina nanoparticles on both filler dispersion and the final properties of the resulting adhesive nanocomposites have been investigated. A tetraglycidyldiaminodiphenylmethane (TGDDM) epoxy resin and three sample series of nanocomposites were prepared via in-situ incorporation of alumina nanoparticles into the reactor. The alumina/TGDDM nanocomposites were prepared individually using neat or non-treated alumina nanoparticles and two kinds of silane-grafted alumina nanoparticles, i.e., APS-treated alumina and GPS-treated alumina. The presence of different alumina nanoparticles in the epoxy matrices resulted in different states of nanofiller dispersion as revealed in SEM and AFM micrographs. It was elucidated that the silane treatment on alumina nanoparticles is crucial for the desired dispersion in the epoxy matrix. Besides, the appropriate filler dispersion resulted in improved thermal resistance and high degree of cure, especially for the adhesive nanocomposite containing APS-treated alumina nanoparticles. In adhesion tests, the shear strength was improved in both nanocomposites containing silane-grafted alumina with more pronounced values for the nanocomposite containing APS-treated alumina nanoparticles. The shear strength reached from 6.6 MPa for the neat epoxy adhesive to 10.2 MPa for the adhesive nanocomposite containing 5 wt % APS-treated alumina nanoparticles mainly due to high levels of dispersion of the high modulus alumina nanoparticles and effective interfacial interactions with the epoxy matrix. The adhesive peel strength of alumina/TGDDM nanocomposites showed a similar trend as in shear strength with more pronounced variations. A noticeable increase in the peel strength of the nanocomposites containing silane-grafted alumina nanoparticles appeared to correlate with greater levels of crack deflection and hence dissipation of fracture energy as observed in SEM pictures.     

苯乙烯-异戊二烯嵌段聚合物热熔压敏胶性能影响因素探讨

用不同种类增粘树脂、不同牌号苯乙烯-异戊二烯嵌段聚合物(简称SIS)制备SIS热熔压敏胶,考察不同种类增粘树脂、不同牌号SIS及萜烯树脂含量对SIS热熔压敏胶性能的影响,结果表明:萜烯树脂是改性SIS热熔压敏胶适宜的增粘树脂,当萜烯树脂在SIS热熔压敏胶中含量达50%时,SIS热熔压敏胶性能较佳,随不同牌号SIS中两嵌段SI含量的增加,SIS热熔压敏胶的剥离强度有所增加,持粘力有所下降。     

Glass lap joints with UV-cured adhesives: Use of a perfluoropolyether methacrylic resin in the presence of an acrylic silane coupling agent

In this work the adhesion to glass of a UV-curable resin with a high fluorine content, namely a methacrylic resin based on perfluoropolyether (PFPE) chains, was studied. In particular, focus was on how the presence of a silane coupling agent, with an acrylate functional group, used either for functionalizing the glass substrates or as an additive to the resin formulations, influenced such adhesion. The adhesive bond strength in shear of lap joints and their resistance to a humid environment and water were assessed. The silane was found to enhance the adhesive strength of the PFPE resin joints, and the silanization of glass proved to be more efficient than the addition of the additive into the formulations. The results were compared to those obtained with a fluorine free acrylic resin. Although the adhesion strength of the PFPE resin was lower compared to that of the fluorine free resin, it showed a better resistance to water as the hydrophobicity of the PFPE chains hindered the transport of water molecules at the resin/glass interface.     

溶胶-凝胶法聚丙烯酸丁酯/二氧化硅杂化材料弹性体的制备与表征

用丙烯酸丁酯与少量功能单体共聚,合成了分子链侧基带羟基的聚丙烯酸丁酯(PBA)乳液,然后与硅溶胶混合,用溶胶-凝胶法制备了PBA/SiO2杂化材料弹性体;研究了SiO2含量对杂化材料弹性体力学性能及透光率的影响,并用扫描电子显微镜、傅里叶变换红外光谱、差示扫描量热分析和动态力学性能分析对杂化材料弹性体的结构进行了表征。结果表明,PBA/SiO2杂化材料热压后成为一种力学性能优良的具有一定透光率的弹性体。随着SiO2含量的增加,杂化材料弹性体的力学性能提高,透光率和SiO2粒子的粒径增加,PBA基体的玻璃化转变温度和损耗因子下降;PBA共聚物分子链侧基所带羟基与SiO2粒子表面的硅醇基发生了缩合脱水反应,形成了Si—O—C共价键,使PBA基体与SiO2粒子构成的界面结合紧密,从而赋予杂化材料弹性体以优良的性能。