Physico-Chemical Criteria for Maximum Adhesion. Part II: A New Comprehensive Thermodynamic Analysis

In this paper, two parameters defined as the relative work of adhesion [W_A/γ_L] and the relative interfacial energy [γ_SL/γ_L] have been examined for their assumed usefulness in correlating the thermodynamic properties of the components of the system substrate/ adhesive with its practical performance (strength). It is shown that the minimum value of [γ_SL/γ_L] relevant to conditions for the maximum adhesion becomes zero only for those systems (relatively rare) for which interaction factor Φ₀ is equal to 1.0.

Several transition points were identified for boundary conditions acquired at θ = 0° and θ = 90° which can be used to predict the properties and performance of an adhesive joint. These transition points are: a_MIN—energy modulus of the system (E. M. S.), relevant to the minimum interfacial energy; a_S—E. M. S. where self-spreading of adhesive occurs; a_CRIT—E. M. S. relevant to conditions under which the thermodynamic work of adhesion becomes negative and the system exhibits a tendency for self-delaminating or has “zero-strength”; a_CF—E. M. S. beyond which the geometry of the interface at any interfacial void or boundary of the joint may be regarded as a crack tip.

It is shown that only in those systems for which Φ₀ = 1.0 can a minimum contact angle of 0° indicate a condition for the maximum strength. If Φ₀ is known, the optimum contact angle can be estimated and hence the optimum surface energy of the substrate (adjusted by surface treatment, etc.) for the maximum adhesion.     

Interface/interphase engineering of polymers for adhesion enhancement: Part II. Theoretical and technological aspects of surface-engineered interphase-interface systems for adhesion enhancement

Part I of this paper reviewed the theoretical principles of the macromolecular design of polymer interface/interphase systems for obtaining maximum adhesion and fracture performance of adhesively bonded assemblies. In Part II a novel, relatively simple and industry-feasible technology for surface-grafting connector molecules is demonstrated and discussed in detail and supported by a range of experimental examples. It is shown, in agreement with contemporary theory, that the use of chemically attached graft chemicals of controlled spatial geometry and chemical functionality enables a significant increase in the strength and fracture energy of the interphase, to the point of cohesive fracture of the substrate, or that of an adjacent medium such as adhesive, elastomer, or other material. This occurs even after prolonged exposure of investigated systems to adverse environments such as hot water.     

Optimum Polymer - Solid Interface Design for Adhesion Strength: Carboxylation of Polybutadiene and Mixed Silanes Surface Modification of Aluminum Oxide

To understand the optimum design of polymer-solid interfaces for adhesion strength, model polymer-solid interfaces of carboxylated polybutadiene(cPBD) adhered to mixed silane modified Al₂O₃ surfaces were examined. The cPBD, having various ?COOH sticker group concentration φ(X) (0 ～ 10 mol%), was synthesized through high-pressure carboxylation of PBD, while Al₂O₃ surfaces were modified to have various -NH₂ density, φ(Y) (0 ～ 100 mol%), using self-assembly of mixed amine- and methyl-terminated silanes. The coadsorption kinetic model of the two silanes was analyzed through X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), and dynamic contact angle (DCA), which gave the capability of controlling the receptor concentration of aluminum oxide surfaces. The polymer surface chain responses after exposure to various media were understood by measuring contact angle changes of various probe liquids. T-peel tests of the model polymer–solid interfaces, as a function of time and sticker and receptor group concentrations showed much longer time dependence than the characteristic time of a bulk polymer chain. Additionally, the classical equation of interface failure was re-examined to see the effects of deformation rate, annealing temperature, and annealing time. A simple scaling analysis of free energy of an adsorbed polymer on a solid surface was extended to predict the adhesion potential of the model polymer–solid interfaces. From the experiments and theory of adhesive vs. cohesive failure, it was found that there existed an optimum product value r* = φ(X)φ(Y)χ of sticker concentration φ(X), receptor concentration φ(Y), and their interaction strength χ, which was approximately 150 cal/mol for this polymer–solid interface. Below or above this optimum product value r*, the fracture energy of polymer-solid interfaces, G _IC, was less than its optimal value, G _lc*.     

Hydrogen Bonding and the Interfacial Component of Adhesion: Acid/Base Interactions of Corona-Treated Polypropylene

The effect of activation of the surface of polypropylene sheet, by a corona discharge, upon the contact angles of liquids and on the surface free energy parameters γ^LW, γ^⊕ and γ^⊖, was determined. Both advancing and retreating contact angles were measured. The “acid/base” theory of the components of surface free energy was employed.

The contact angles of water and glycerol were initially lower by as much as 30°, after treatment, and that of diiodomethane was lower by about 5°. With time, the advancing angles rose, and the γ^⊕ and γ^⊖ parameters fell, towards the values on the untreated solids, and attained more or less steady values after 5 to 10 days. The basic component, γ^⊖, was the most strongly affected by the corona treatment; it rose, typically, from 2.2 to as high as 25 mJ/m². The acidic component, γ^⊕, rose from zero to as high as 1.9 mJ/m². Its decay with time was only qualitatively the same as that of γ^⊖. The retreating angles, and the corresponding energy components, were changed in the same direction, and somewhat more strongly, than were the “advancing” data.

The well-known improvement in the property of forming strong joints or adherent coatings, after corona treatment, is no doubt due to the formation of sites or areas on the polymers where hydrogen bonds can be formed. The decay of the strength of adhesion with time is, no doubt, due to the decay of these sites or areas.     

A new method for the detection of microorganisms in blood cultures: Part I. Theoretical analysis and simulation of blood culture processes

The physical and chemical changes occurring in blood as a consequence of microbial activity can be used as quantitative indicators of the presence of microorganisms in blood cultures. This paper reports on the theoretical analysis and computer simulation of the changes in the physical and chemical properties of blood expected as a result of the presence of microorganisms and explores the possibilities of spectrophotometric systems for the early detection of pathogens. It is concluded that multi‐wavelength reflectance methods are suitable and that the approach reported herein can lead to considerable simplifications and cost reduction of blood culture systems.     

Base case process development for energy efficiency improvement, application to a Kraft pulping mill. Part I: Definition and characterization

The development of a base-case process is a fundamental step in an energy efficiency study to obtain reliable results. However, this step is often overlooked and there are no clear guidelines for the systematic development of the base-case. A methodology has been proposed to properly define and evaluate the complete process for a subsequent in-depth energy analysis. It consists of two stages: definition and characterization of the process, and benchmarking analysis. In this paper, the first stage is presented. The base-case should encompass the process and the utilities systems, i.e., steam and water, as they are the driving forces of the chemical transformations. A four-pronged procedure is proposed to properly define and characterize a process and its utilities: data gathering, master diagram construction, utilities systems analysis, and simulation. The main objective is to build a computer simulation model to provide detailed information on production, distribution, utilization and post-utilization treatment of steam and water. Process inefficiencies are also identified, such as the low condensate recovery or the presence of non-isothermal mixing points. The procedure has been applied to an operating Kraft pulping mill in Eastern Canada.