Adhesion and Failure Mechanisms of a Model Hot Melt Adhesive Bonded to Polypropylene

A model hot melt adhesive (HMA) based on an ethylene/vinyl acetate copolymer (EVA), an Escorez® hydrocarbon tackifier, and a wax has been used to bond together polypropylene (PP) films to give equilibrium bonding. Peel strengths were determined over a broad range of peel rates and test temperatures. Contrary to the peel behavior of joints with simple rubbery adhesives [1], peel strengths with this semi-crystalline adhesive are not rate-temperature superposable, and multiple transitions in failure locus occur. The semi-crystalline structure of the HMA also prevents rate-temperature superposition of its dynamic moduli.

At different test temperatures, the dependence of peel strength on peel rate shows some resemblance to the dependence of the loss tangent of the bulk adhesive on frequency. This is consistent with a previous result [2] that the HMA debonding term. D, varies with the loss tangent of a HMA at the T-peel debonding frequency.

This model HMA, similar to block copolymer/tackifier blends [3], consists of two phases: an EVA-rich and a tackifier-rich phase, in its amorphous region. At a low peel rate of 8.33 × 10^-5 m/s, the peel strength shows a maximum at a temperature that corresponds to the transition temperature of the tackifier-rich phase (T₁). At a higher peel rate of 8.33 × 10^-3 m/s, the peel strength rises with increasing test temperature, but becomes essentially constant at temperature T₁'. It is believed that, to optimize the peel strength of a HMA at ambient temperature, it is advantageous to formulate the EVA polymer (or other semi-crystalline polyolefins) with a compatible tackifier that yields a tackifier-rich phase with a transition temperature (T₁') in the vicinity of room temperature.     

Correlation between equation of state and temperature and pressure dependence of self-diffusion coefficient of polymers and simple liquids

Correlation between the equation of state and the temperature dependence of the self-diffusion coefficient D for polymers such as polystyrene (PS) and polydimethyl siloxane (PDMS) and simple liquids such as argon, methane and benzene and the pressure dependence of D for oligomers such as dimethyl siloxane (DMS) and simple liquids such as cyclohexane and methanol has been examined based on the equation of state derived previously. The experimental data used were published by Antonietti et al. and McCall et al. for polymers, by McCall for linear dimethylsiloxanes and by Jonas et al. and Woolf et al. for simple liquids. The expression for D in this work is given by

where A₁(M) is a function of molecular weight M_w, C₁(T) and P₁(T) are functions of temperature and B₁, n₁ and m₁ are constants determined experimentally. For simple liquids, the values of n₁ obtained range from 0.3 to 1.2, with an average , and m₁ is in the range 0.5–1.2, with . For polymers, values of n₁ are in the range 2.5–7.0 for PS and 0.5–1.3 for PDMS and m₁ for DMS is in the range 0.8–1.0. The relation Dη/T = f(M) is found to be useful for simple liquids over a wide range of temperature including the critical region and for pressures up to ≈5 kbar

1 kbar = 100 MPa There is a close correlation between ln(D/T) and _p and β_T through ln(D/T)ln D_c−⁻¹_p−β⁻¹_T, where D_c is D at the critical temperature and _p and β_T are the thermal expansion coefficient and compressibility, respectively. The molecular weight dependence of D for polymers and simple liquids is discussed based on the experimental data and recent theory of Doi and Edwards. A new model for the mechanism of self-diffusion in the liquid state is proposed.     

优筋布置矩形箱体应力及变形分析

针对工业生产中矩形箱体笨重、加筋结构布置设计欠佳的问题,采用ANSYS APDL语言对矩形箱体进行静压工况下应力及变形分析。选取6因素5水平正交试验方案,以矩形箱体最大一次应力S_1max、最大等效应力S_2max以及最大变形量Δ_max作为试验指标,侧壁加强铁间距A、宽度B及厚度C,端壁加强铁间距D、宽度E及厚度F作为试验因素,结合矩阵分析法获得加强筋的优筋布置方案A₄B₅C₅D₂E₅F₂,并用ANSYS一阶优化算法对箱壁以及箱壁加强铁壁厚进行优化。结果表明:矩形箱体采用优筋布置后,箱体质量减少了27%。最后采用极限载荷分析法通过P_T=0.1 MPa试验工况验证。     

The glass temperature of polymer blends

The entropy theory of glasses is used to derive the glass temperature, T_g, of a binary polymer blend in terms of the glass temperatures of the two substituents. The formula is T_g = B₁T_g1 + B₂T_g2, where B_i is the fraction of flexible bonds of substituent i. A bond is flexible if rotation about it changes the shape of the molecule. Bonds in side groups as well as in the backbone are to be counted. This formula assumes that the free volume, taken here to be the volume fraction of empty lattice sites, is the same for each of the three materials. It has no parameters. The above equation expressed in weight fractions, W_i, is (T_g − T_g1)W₁(γ₁/ω₁) + (T_g − T_g2)W₂(γ₂/ω₂) = 0, where ω_i is the weight of a monomer unit and gg_i is the number of flexible bonds per monomer unit. A more general treatment is given. One variation of the more general treatment which expresses the properties of the blend in purely additive terms gives T_g = B₁T_g1 + B₂T_g2 + KB₁B₂(T_g1 − T_g2)(V₀₁ − V₀₂), where V_0i are the free volume fractions of the homopolymers at their glass temperatures and K is a constant. The added term is usually small. The most general form of the equation requires the energy of interaction between the two unlike molecules, which can be estimated by volume measurements on the blend.     

正弦波纹挡板式沉降器内流动特性

采用VOF模型对正弦波纹式入口挡板的重力非均相沉降器内流场进行数值模拟研究。对比了正弦波纹挡板与平挡板的平均流场分布情况,分析了沉降器的轴向流速均一程度（λ₁）随时间演化特性,探究了λ₁和面积加权平均湍流强度（I_a）在沉降器内空间分布特性;引入流场均稳指标USC,研究了冲击间距（L_b/D）对USC的影响。结果表明：正弦波纹挡板作为入口构件可以有效降低返混。在0.84＜L_b/D＜2.17范围内,正弦波纹板沉降器内流场的均一程度整体高于平面挡板;随着L_b/D减小,平挡板沉降器内流场的λ₁基本不变,但正弦波纹挡板沉降器内流场的λ₁降低,且对I_a的影响不明显。对比平挡板,正弦波纹挡板可以有效降低轴向速度的梯度,使返混区面积减小,流场稳定性提高。随着L_b/D增加,USC值呈现多峰值趋势,L_b/D=2.17时正弦波纹板沉降器的USC取得极大值为14.68,较平挡板提高了93.67%。     

Pressure Sensitive Adhesives Based on VectorR SIS Polymers I. Rheological Model and Adhesive Design Pathways

Dexco Polymers (a Dow/Exxon partnership) has been manufacturing Vector^R SIS polymers since 1990.¹ This paper describes experiments carried out to study Vector SIS polymers and model pressure sensitive adhesive (PSA) formulations based on Exxon Chemical's Escorez^R 1310LC tackifier. The adhesive behavior of tackified polymers was quantitatively analyzed by applying the rheological principle of time-temperature superposition² and the mapping approach,^3,4 and the pressure sensitive rheological model⁵ developed earlier. This model⁵ was developed by expanding and modifying an equation [adhesive fracture strength = (intrinsic adhesion) × (bulk energy dissipation)] proposed by Gent et al.^6,7 and Andrews et al.^8,9 This study delivers two key results. The first is that the fracture strength of the PSA/steel bond is the multiplication of three terms: the intrinsic (or interfacial) adhesion, the bonding and the debonding terms (Fig. 1). The debonding term is correlated with the logarithm of the loss modulus at the PSA debonding frequency or with the logarithm of the monomeric friction coefficient of the block copolymer/tackifier system. Both the loss modulus and the monomeric friction coefficient measure the energy dissipation in the bulk adhesive. The second is that PSA design pathways can be established by a mapping approach in the rheological space of the plateau modulus versus the loss modulus peak position in the frequency scale (Fig. 2). Plateau modulus is the bonding parameter because it measures the wetting capability of the adhesive with the substrate surface. The loss modulus peak position is the debonding parameter because it corresponds approximately to the time scale (or the frequency scale) in which one deforms the adhesive to maximize energy dissipation. Therefore, the tackifier and oil combination lowers the plateau modulus, but increases the T_g of the polyisoprene phase of the SIS polymer. This increase in T_g is equivalent to the lowering of the rate of local rearrangement (frequency of segment jumps) of the polyisoprene chains of the block copolymer. An optimal “tackification pathway” in this rheological space is achieved by tailoring the tackifier type and T_g, and the amount of oil used in the PSA.

In brief, the PSA rheological model and mapping approach described in this work for Vector SIS polymers give a comprehensive understanding and adhesive design pathways. This concept and approach not only allow raw material suppliers to improve and design better tackifier and polymer products, but also provide PSA formulators a quantitative tool to achieve PSA end property results.     

An experimental study of immiscible liquid–liquid dispersions in a pump–mixer of mixer–settler

Drop size distribution(DSD) or mean droplet size(d32) and liquid holdup are two key parameters in a liquid–liquid extraction process. Understanding and accurately predicting those parameters are of great importance in the optimal design of extraction columns as well as mixer–settlers. In this paper, the method of built-in endoscopic probe combined with pulse laser was adopted to measure the droplet size in liquid–liquid dispersions with a pump-impeller in a rectangular mixer. The dispersion law of droplets with holdup range 1% to 24% in batch process and larger flow ratio range 1/5 to 5/1 in continuous process was studied. Under the batch operation condition, the DSD abided by log-normal distribution. With the increase of impeller speed or decrease of dispersed phase holdup, the d32 decreased. In addition, a prediction model of d32 of kerosene/deionized system was established as d_(32)/D = 0.13(1 + 5.9φ)We~(-0.6). Under the continuous operation condition, the general model for droplet size prediction of kerosene/water system was presented as d_(32)/D = C_3(1 + C_4φ)We~(-0.6). For the surfactant system and extraction system, the prediction models met a general model as d_(32)/D = bφ~nWe~(-0.6).     

运用粒子图像测速仪研究双层桨搅拌槽内流体流动

The flow fields in a dual Rushton impeller stirred tank with diameter of 0.48 m （T） were measured by using Particle Image Velocimetry （PIV）. Three different size impellers were used in the experiments with diameters of D = 0.33T, 0.40T and 0.50T, respectively. The multi-block and 360° ensemble-averaged approaches were used to measure the radial and axial angle-resolved velocity distributions. Three typical flow patterns, named, merging flow, parallel flow and diverging flow, were obtained by changing the clearance of the bottom impeller above the tank base （C1） and the spacing between the two impellers （C2）. The results show that while C1 is equal to D, the parallel flow occurs as C2≥0.40T, C2≥0.38T and C2≥0.32T and the merging flow occurs as C2≤0.38T, C2≤0.36T and C2≤0.27T for the impellers with diameter of D=0.33T, 0.40T and 0.50T, respectively. When C2 is equal to D, the diverging flow occurs in the value of C1≤0.15T for all three impellers. The flow numbers of these impellers were calculated for the parallel flow. Trailing vortices generated by the lower impeller for the diverging flow were shown by the 10° angle-resolved velocity measurements. The peak value of turbulence kinetic energy （ k/V^2tip = 0.12-0.15 or above） appears along the center of the impeller discharging stream.     

乙烯-醋酸乙烯基钢质管道防腐用热熔胶的研究

以EVA树脂为主体树脂制备钢质管道防腐用热熔胶,选用聚合松香为增粘剂,聚异丁烯为增韧剂,研究了不同VA含量、不同熔体指数的EVA树脂、聚合松香及聚异丁烯对热熔胶环球软化点、脆化温度和剥离强度等性能的影响。     

高效水密封防腐绝缘热熔胶的研究

以EVA树脂为主体树脂制备高效水密封防腐绝缘热熔胶,选用热塑性酚醛树脂代替松香作为增粘剂,聚异丁烯为增韧剂,研究了不同EVA树脂、热塑性酚醛树脂及聚异丁烯对热熔胶环球软化点、脆化温度和剪切强度等性能的影响。     

Heat Resistance Evaluation of Adhesive Joints in Terms of Stability Loss Temperature

The characteristics of evaluation of heat resistance of adhesive joints, i.e. the stability loss temperature (T_T8) is suggested. Theoretical base of this characteristic is that heat resistance should be regarded as durability, in dependence with loading and temperature change law.

Stability loss temperature is determined according to the principle of thermomechanical testing. The investigations showed that there is a relationship between stability loss temperature, loading and the thickness of the adhesive layer. This relationship for adhesive joints of soft materials has a hyperbolic form.

If for adhesive joints the principle of superposition of destructions (Bailey criterion) exists, then, having durability equations, the stability loss temperature may be determined by calculation.     

Viscoelastic and adhesion properties of EVA/tackifier/wax ternary blend systems as hot-melt adhesives

Two types of wax were added to a ethylene vinyl acetate (EVA) copolymer/aromatic hydrocarbon resin (tackifier) blend in the molten state and the miscibility, viscoelastic and adhesion properties of ternary blends as hot-melt adhesives (HMAs) were investigated. Miscibility and viscoelastic properties were studied using differential scanning calorimetry (DSC), Brookfield viscometry and dynamic mechanical thermal analysis (DMTA), and their adhesion strength was determined in terms of single lap shear strength. DSC thermograms of both types of waxes showed their melting peaks in a similar region to that of EVA/tackfier blend. It was difficult to evaluate the miscibility of ternary blends using DSC because the melting peaks of the waxes overlapped with those of the EVA/tackifier blend, although the glass transition temperature (T _g) of the ternary blend systems slightly increased with increasing wax concentration. However, their storage modulus (E′) increased slightly and loss tangent (tan δ) showed different peaks when two types of wax were added to the EVA/tackifier blend. Therefore, the miscibility of EVA/tackifier blend altered with addition of waxes. In addition, their melt viscosity decreased with increasing wax concentration. Furthermore, the adhesion strength of the ternary blends decreased with increasing wax concentration, despite the increment of storage modulus. These results suggested that the ternary blends of EVA/tackifier/wax were heterogeneous.     

New and Improved Tests for Adhesion

Three new methods are discussed for measuring the work G_a, required to detach unit area of an adhering material from a substrate. The first is a simple modification of the Outwater double-torsion test for long rectangular plates, bonded together. This method is suitable for evaluating aluminum-epoxy bonds, for example, or the transverse strength of fibrous composites. The second is a pull-off test for long strips adhering to a rigid surface. It seems suitable for adhesive tapes and laminates. The third is a reconsideration of the “blister” test for films and coatings, in which a circular debond at the interface is made to grow by internal pressure. The relation obtained between pull-off force F for a strip, or blow-off pressure P for a layer, takes the unusual form:

F⁴ (or P⁴) ∞ KG³_a

where K is the tensile stiffness of the detaching layer. This dependence arises from the non-linear (cubic) relation between load or pressure and deflection in these configurations. Nevertheless, the product Fθ, where θ is the angle of detachment of a strip, or Py, where y is the height of a “blister”, give direct measures of the strength of adhesion G_a, independent of the stiffness of the adhering material and of the extent of detachment.     

Adsorption of methane/ethane mixtures on dry coal at elevated pressure

The binary adsorption characteristics of methane and ethane on dry coal to 40 atm pressure have been calculated from pure-component isotherms. In some coal seams, pressures exceeding 40 atm have been recorded and the methane sampled from the virgin coal often shows a few percent of ethane. The binary adsorption characteristics were calculated by employing the ideal adsorbed solution theory of Myers and Prausnitz, and experimentally-determined (Type I) pure gas isotherms at 0, 30 and 50 °C. The coal used in this investigation was high-volatile ‘A’ bituminous (hvab) from the Pennsylvania Pittsburgh seam. Gas nonideality was accounted for by replacing pressure with fugacity. Adsorption of methane on dry coal is purely physical; the isosteric heat of adsorption does not exceed 2.4 kcal/mol^* at 30 °C on the above coal. Isobars on the resulting binary equilibrium diagram exhibited an unexpected phenomenon of intersecting each other which might be attributable to the above nonideality considerations. The region of a few percent of ethane, which is of practical importance from the viewpoint of coal seams, was expanded and reduced to an equation: V(CH₄) = −21.52 + 7.18(VF) + 16.88(VF)² −0.395(P) − 0.00661(P)² + 0.824(T) − 0.00030(T)² + 0.928(VF)(P) − 0.858(VF)(T). V(Total) = 25.9 − 23.6(VF) + 0.655(P) − 0.00875(P)² − 0.795(T) + 0.743(VF)(T) where V(CH₄) and V(Total) = cm³(STP)CH₄ and total gas respectively adsorbed per g dry coal; VF = vol. fraction of methane as analysed at 1 atm (0.94 VF 1.0); P = seam pressure, atm (0 P 40); T=seam temperature, °C(−10 T 50).     

Tracer diffusion of aromatic hydrocarbons in n-hexane up to the supercritical region

Tracer diffusion coefficients are determined with the Taylor-Aris dispersion method for benzene, toluene, p-xylene, mesitylene, naphthalene and phenanthrene in liquid n-hexane along the vapour-liquid coexistence curve from 333.2 to 485.4 K and in supercritical n-hexane at 507.4, 522.0, 533.3, 543.2K and several pressures. A rough-hard-sphere model is found to represent quite well (to within ± 6%) the observed tracer diffusivities in the density region where computer simulation results for D₁₂^SHS/D₁₂^E are available, i.e. 1.5 V/V₀ 3. Furthermore, Hildebrand's free volume model together with the excluded-volume effect provides the basis for a general linear relationship between D₁₂V_C12 and V for tracer diffusion in liquid n-hexane up to its critical temperature. For diffusion in the supercritical region two definitions of reduced tracer diffusivity, one based on the rough-hard-sphere theory of tracer diffusion and the other on the extension of Helfand-Rice corresponding state principle for self-diffusion, permit generalized correlations that are capable of representing the experimental results in both supercritical n-hexane and carbon dioxide to within ±4% on average.     

新能源汽车电池用无镁储氢合金的制备与性能研究

采用真空电弧熔炼和925 ℃/12 h退火的方法制备了Y_1-xLa_xNi_3.25Al_0.15Mn_0.15储氢合金（x=0~1）,研究了x值对储氢合金物相组成和电化学性能的影响。结果表明,x=0和0.15的储氢合金主要由LaNi₅和Ce₂Ni₇相组成,x=0.25、0.33和0.5储氢合金主要由Ce₅Co₁₉和Ce₂Ni₇相组成,x=0.75和1储氢合金主要由PuNi₃、LaNi₅和Ce₂Ni₇相组成;相同充放电循环周次下,x=0.15~1储氢合金的放电容量和抗氢致非晶化能力都高于x=0储氢合金,且随着x从0增加至1,储氢合金的最大放电容量（C_max）、容量保持率（S₁₀₀）、氢扩散系数（D₀）和高倍率放电性（HRD₉₀₀）都呈现先增加后减小趋势,在x=0.33时取得C_max、S₁₀₀、D₀和HRD₉₀₀最大值。Y_1-xLa_xNi_3.25Al_0.15Mn_0.15储氢合金的循环稳定性与合金电极的耐腐蚀性密切相关,高倍率放电性能取决于储氢合金的氢扩散速率。     

Miscibility and adhesive properties of ethylene vinyl acetate copolymer (EVA)‐based hot‐melt adhesives. I. Adhesive tensile strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that are made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of typical miscibility types and measured their adhesive tensile strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of adhesive tensile strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the glass transition temperature (T_g) of the blends that became higher as tackifier content of blends increased when blend components were miscible. In terms of HMA performances, we suggest that factors other than miscibility affect absolute values of adhesive tensile strength more directly than miscibility; this idea has to be investigated further in a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 719–725, 2002     

基于XCT的气固流化床布风板射流特征研究

构建了X光层析成像（XCT）气固流动参数测量系统,基于锥形束滤波反投影算法（FDK）开发了CT三维重建软件,并设计了射流识别及量化算法。基于以上方法获得了不同流化风速下床料粒径d_p、布风板孔口直径d₀和布风板孔口均分面积A₀对射流形态结构和几何特征的影响规律。结果表明平均射流长度L、最大直径D和体积V与床料粒径d_p成反比,与孔口直径d₀和孔口均分面积A₀成正比,最终拟合了流化床平均射流长度关联式。     

Thermal,viscoelastic and adhesion properties of EVA (ethylene-co-vinyl acetate) hot melts containing polypropylene waxes of different nature

Wax determines the compatibility of tackifier and polymer in hot melt adhesives. Although the influence of the addition of microcrystalline and Fischer-Tropsch waxes on the properties of ethylene-co-vinyl acetate (EVA) hot melts has been studied, the addition of polypropylene wax has not been considered yet. In this study, different polypropylene waxes (polypropylene wax – PP, – maleic anhydride grafted polypropylene wax – PPMA – copolymer of polypropylene and 10.9?wt.% polyethylene wax – PP-E) were added to EVA hot melts and they were characterized by Brookfield viscosity, softening point measurement, differential scanning calorimetry, thermal gravimetric analysis, dynamic mechanical thermal analysis, plate–plate rheology, tack, and single-lap shear adhesion. The viscosities of EVA hot melts containing polypropylene waxes were relatively high, the highest viscosity corresponded to the formulation containing PP-E wax which also showed pseudoplasticity. The change in viscoelastic properties (i.e., from dominantly viscous to dominantly elastic) was produced at lower temperature in EVA hot melt containing PP-E wax, this adhesive exhibited the highest tack. On the other hand, the addition of acrylic PPMA wax increased the adhesion of EVA hot melt but lower tack was obtained. Finally, the PP-E wax was more compatible with EVA copolymer than the other polypropylene waxes.     

Primers for Bonding Polyolefin Substrates with Alkyl Cyanoacrylate Adhesive

Polyolefins, such as polypropylene and polyethylene, are among the most commonly-utilized plastics in the world, but, because of their non-polar surfaces, are among the most difficult to bond with adhesives. A surface treatment is required before adhesive application to achieve good adhesion.

Alkyl cyanoacrylates are widely used instant adhesives, e.g. Super Glue^®, for bonding a variety of substrates, such as metal, plastics, glass, wood, and leather. It would be desirable to bond polyolefins with these adhesives because of their availability and ease of use. Amines and ammonium carboxylates, possessing long alkyl chains, were evaluated as adhesion promoting primers for alkyl cyanoacrylate adhesives on polyolefins.

Among trialkyl amines, trialkylammonium carboxylates, and tetraalkylammonium carboxylates, trialkylammonium carboxylate primers produced an adhesive bond so strong that the failure occurred at the polyolefin substrate. Trialkylammonium carboxylate primers also demonstrated excellent performance retention over prolonged atmospheric exposure prior to application of the adhesive. Trialkyl amines and tetraalkylammonium carboxylates also promoted adhesion but lost maximum effectiveness on exposure to the atmosphere. The cause of the deterioration in amine primer effectiveness over prolonged exposure was identified to be trialkylammonium bicarbonate formation and/or diffusion of the primer into the polyolefin surface.