Enhancing the carbonation of MgO cement porous blocks through improved curing conditions

The use of reactive magnesia (MgO) as the binder in porous blocks demonstrated significant advantages due to its low production temperatures and ability to carbonate, leading to significant strengths. This paper investigates the enhancement of the carbonation process through different curing conditions: water to cement ratio (0.6-0.9), CO2 concentration (5-20%), curing duration (1-7 days), relative humidity (55-98%), and wet/dry cycling frequency (every 0-3 days), improving the carbonation potential through increased amounts of CO2 absorbed and enhanced mechanical performance. UCS results were supported with SEM, XRD, and HCl acid digestion analyses. The results show that CO2 concentrations as low as 5% can produce the required strengths after only 1 day. Drier mixes perform better in shorter curing durations, whereas larger w/c ratios are needed for continuous carbonation. Mixes subjected to 78% RH outperformed all the others, also highlighting the benefits of incorporating wet/dry cycling to induce carbonation. © 2014 Elsevier Ltd.

ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

Thermoplastic Elastomers Based on Compatibilized Poly(butylene terephthalate) Blends: Effect of Functional Groups and Dynamic Curing

Two sets of graft copolymers were prepared by grafting glycidyl methacrylate (GMA) or ally] (3-isocyanate-4-tolyl) carbamate (TAI) onto ethylene/propylene/diene terpolymer (EPDM) in an internal mixer. These graft copolymers were used as the compatibilizer to prepare the thermoplastic elastomers (TPEs) containing 50 wt%, of poly(butylene terephthalate), PBT, 30 wt% of compatibilizer, and 20 wt% of nitrile-butadiene rubber, NBR. The indirect, two-step mixer process was chosen for dynamic curing.

Combined Effects of Hot Curing Conditions and Reaction Heat on Rubber Vulcanization Efficiency and Vulcanizate Uniformity

A mathematical model of the chemical kinetics of silicone rubber Vulcanization is developed, with the thermal effects being computed using the increment method, and the hot Vulcanization process estimated with the finite element method. The results show that the reaction heat of rubber vulcanization is important for energy saving, and that a proper curing medium temperature is important when considering both vulcanization efficiency and vulcanizate uniformity. The results also indicate that increases in the forced convective heat transfer coefficient have no significant effect above a certain level. The validity of the numerical model is indirectly proven by comparison with existing data.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .1. DSC characterization of curing reaction

The curing reaction process of epoxy-terminated poly(phenylene ether ketone) (E-PEK) with 4,4'-diaminodiphenyl sulfone (DDS) and hexahydrophthalic acid anhydride (Nadic) as curing agents was investigated using isothermal differential scanning calorimetry (IDSC) and nonisothermal differential scanning calorimetry (DDSC) techniques. It was found that the curing reactions of E-PEK/DDS and E-PEK/Nadic are nth-order reactions but not autoaccelerating. The experimental results revealed that the curing reaction kinetics parameters measured from IDSC and DDSC are not equivalent. This means that, in the curing reaction kinetics model for our E-PEK system, both isothermal and nonisothermal reaction kinetics parameters are needed to describe isothermal and nonisothermal curing processes, The isothermal and nonisothermal curing processes were successfully simulated using this model. A new extrapolation method was suggested. On the basis of this method the maximum extent of the curing reaction (A(ult)) that is able to reach a certain temperature can be predicted. The A(ult) for the E-PEK system estimated by the new method agrees well with the results obtained from another procedure reported in the literature. (C) 1997 John Wiley & Sons, Inc.

PROMOTER EFFECT OF HALOGEN ANIONS ON THE DIRECT ELECTROCHEMICAL REACTION OF CYTOCHROME-C AT GOLD ELECTRODES

The promoter effect of halogen anions for heterogeneous electron transfer between cytochrome c and a gold electrode was studied. It was found that the order of the promoter ability of halogen anions is I- > Br- > Cl- > F-. In addition, factors which can affect the promoter effect were discussed.

Chemistry of B1- and B10- boranes containing halogen or pseudohalogen groups

The research described in this thesis involved the chemistry of borane-species which contain one or more halide or pseudohalide groups. Both monoboron species e.g. [BH3X]- and "cluster" borane species e.g. [B10H9X]2- and I-Se B11H10 were studied. The first chapter is a review of the syntheses, properties and reactions of halide and pseudohalide species containing from one to ten boron atoms. Chapter Two is a theoretical investigation of' the electronic and molecular structures of two series of boranes i. e. [BH3X]- and [B10H9X]2- where X = H, CI, CN, NCS, SCN and N3. The calculational method used was the Modified Neglect of Differential Overlap (MNDO) method of Dewar et al. The results were compared where possible with experimental results such as the X-ray crystallographically determined structures of [BH3CI]- and [B10H10]2-. Chapter Three concerns halogenated selenaborane clusters and reports an improved synthesis of 12-Br-SeB11H10 and the first structural data for a simple non-metal containing selenaborane cage with the X-ray crystallographically determined structure of 12-1-SeB11H10. Finally, an indepth n.m.r. study of Se2B9H9 is also reported together with attempts to halogenate this compound. The last two chapters are based on single boron systems. Chapter Four concerns the synthetic routes to amine-boranes and -cyanoboranes from [BH4]- and [BH3CN]- substrates. This chapter discusses some difficulties encountered when polyamines were used in these reactions. The characterisation of an unusual ketone isolated from some of these reactions, the X-ray crystallographically determined structure of 4-dimethylamino-pyridine-cyanoborane and a new route to pyrazabole dimeric species are also discussed. The final chapter reports on work carried out at producing BH2X (X = H, CN) adducts of aminophosphines. Three routes were attempted to generate P-B and N-B bonded species with varying degrees of success. Some unusual products of these reactions are discussed including [Ph2(O) PPPh2 ] [Ph2NH]2, the structure of which was determined by X-ray crystallography.

The effect of curing on the performance of ACF bonded chip-on-flex assemblies after thermal ageing

Purpose – Anisotropic conductive film (ACF) is now an attractive technology for direct mounting of chips onto the substrate as an alternative to lead-free solders. However, despite its various advantages over other technologies, it also has many unresolved reliability issues. For instance, the performance of ACF assembly in high temperature applications is questionable. The purpose of this paper is to study the effect of bonding temperatures on the curing of ACFs, and their mechanical and electrical performance after high temperature ageing. Design/methodology/approach – In the work presented in this paper, the curing degree of an ACF at different bonding temperatures was measured using a differential scanning calorimeter. The adhesion strength and the contact resistance of ACF bonded chip-on-flex assembly were measured before and after thermal ageing and the results were correlated with the curing degree of ACF. The ACF was an epoxy-based adhesive in which Au-Ni coated polymer particles were randomly dispersed. Findings – The results showed that higher bonding temperatures had resulted in better ACF curing and stronger adhesion. After ageing, the adhesion strength increased for the samples bonded at lower temperatures and decreased for the samples bonded at higher temperatures. ACF assemblies with higher degrees of curing showed smaller increases in contact resistance after ageing. Conduction gaps at the bump-particle and/or particle-pad interfaces were found with the help of scanning electron microscopy and are thought to be the root cause of the increase in contact resistance. Originality/value – The present study focuses on the effect of bonding temperatures on the curing of ACFs, and their adhesion strength and electrical performances after high temperature ageing. The results of this study may help the development of ACFs with higher heat resistance, so that ACFs can be considered as an alternative to lead-free solders.

Variable frequency microwave curing of polymer materials in microelectronics packaging applications

The use of variable frequency microwave technology in curing of polymer materials used in microelectronics applications is discussed. A revolutionary open-ended microwave curing system is outlined and assessed using experimental and numerical approaches. Experimental and numerical results are presented, demonstrating the feasibility of the system

Multiphysics simulation of microwave curing in micro-electronics packaging applications

Purpose – This paper aims to present an open-ended microwave curing system for microelectronics components and a numerical analysis framework for virtual testing and prototyping of the system, enabling design of physical prototypes to be optimized, expediting the development process. Design/methodology/approach – An open-ended microwave oven system able to enhance the cure process for thermosetting polymer materials utilised in microelectronics applications is presented. The system is designed to be mounted on a precision placement machine enabling curing of individual components on a circuit board. The design of the system allows the heating pattern and heating rate to be carefully controlled optimising cure rate and cure quality. A multi-physics analysis approach has been adopted to form a numerical model capable of capturing the complex coupling that exists between physical processes. Electromagnetic analysis has been performed using a Yee finite-difference time-domain scheme, while an unstructured finite volume method has been utilized to perform thermophysical analysis. The two solvers are coupled using a sampling-based cross-mapping algorithm. Findings – The numerical results obtained demonstrate that the numerical model is able to obtain solutions for distribution of temperature, rate of cure, degree of cure and thermally induced stresses within an idealised polymer load heated by the proposed microwave system. Research limitations/implications – The work is limited by the absence of experimentally derived material property data and comparative experimental results. However, the model demonstrates that the proposed microwave system would seem to be a feasible method of expediting the cure rate of polymer materials. Originality/value – The findings of this paper will help to provide an understanding of the behaviour of thermosetting polymer materials during microwave cure processing.

Microwave curing for high density package

Summary form only given. Currently the vast majority of adhesive materials in electronic products are bonded using convection heating or infra-red as well as UV-curing. These thermal processing steps can take several hours to perform, slowing throughput and contributing a significant portion of the cost of manufacturing. With the demand for lighter, faster, and smaller electronic devices, there is a need for innovative material processing techniques and control methodologies. The increasing demand for smaller and cheaper devices pose engineering challenges in designing a curing systems that minimize the time required between the curing of devices in a production line, allowing access to the components during curing for alignment and testing. Microwave radiation exhibits several favorable characteristics and over the past few years has attracted increased academic and industrial attention as an alternative solution to curing of flip-chip underfills, bumps, glob top and potting cure, structural bonding, die attach, wafer processing, opto-electronics assembly as well as RF-ID tag bonding. Microwave energy fundamentally accelerates the cure kinetics of polymer adhesives. It provides a route to focus heat into the polymer materials penetrating the substrates that typically remain transparent. Therefore microwave energy can be used to minimise the temperature increase in the surrounding materials. The short path between the energy source and the cured material ensures a rapid heating rate and an overall low thermal budget. In this keynote talk, we will review the principles of microwave curing of materials for high density packing. Emphasis will be placed on recent advances within ongoing research in the UK on the realization of "open-oven" cavities, tailored to address existing challenges. Open-ovens do not require positioning of the device into the cavity through a movable door, hence being more suitable for fully automated processing. Further potential advantages of op- - en-oven curing include the possibility for simultaneous fine placement and curing of the device into a larger assembly. These capabilities promise productivity gains by combining assembly, placement and bonding into a single processing step. Moreover, the proposed design allows for selective heating within a large substrate, which can be useful particularly when the latter includes parts sensitive to increased temperatures.

Comparison of encapsulant curing with convention and microwave systems

Comparison of the performance of a conventional convection oven system with a dual-section microwave system for curing thermosetting polymer encapsulant materials has been performed numerically. A numerical model capable of analysing both the convection and microwave cure processes has been developed and is breifly outliines. The model is used to analyse the curing of a commercially available encapsulant material using both systems. Results obtained from numerical solutions are presented, confirming that the VFM system enables the cure process to be carried out far more rapidly than with the convection oven system. This capability stems from the fundamental heating processes involved, namely that microwave processing enables the heating rate to be varied independently of the material temperature. Variations in cure times, curing rates, maximum temperatures and residual stresses between the processes are fully discussed.

Advanced microwave oven for rapid curing of encapsulant

The curing of a thermosetting polymer materials utilized on micro-electronics packaging applications can be performed using microwave systems. The use of microwave energy enables the cure process to be completed more rapidly than with alternative approaches due to the ability to heat volumetrically. Furthermore, advanced dual-section microwave systems enable curing of individual components on a chip-on-board assembly. The dielectric properties of thermosetting polymer materials, commonly used in microelectronics packaging applications, vary significantly with temperature and degree of cure. The heating rate within a material subjected to an electric field is primarily dependant on the dielectric loss properties of the material itself. This article examines the variation in dielectric properties of a commercially available encapsulant paste with frequency and temperature and the resulting influence on the cure process. The 'FAMOBS' dual section microwave system and its application to microelectronics manufacture are described. The measurement of the dielectric properties of 'Henkel EO1080' encapsulant paste uses a commercially available 'dielectric probe kit' and is described in this paper. The FAMOBS heating system is used to encapsulate a small op-amp chip. A numerical model formulated to assess the cure process in thermosetting polymer materials under microwave heating is outlined. Numerical results showing that the microwave processing systems is capable of rapidly and evenly curing thermosetting polymer materials are presented.

Numerical analysis of thermal stresses induced during VFM encapsulant curing

Encapsulant curing using a Variable Frequency Microwave (VFM) system is analysed numerically. Thermosetting polymer encapsulant materials require an input of heat energy to initiate the cure process. In this article, the heating is considered to be performed by a novel microwave system, able to perform the curing process more rapidly than conventional techniques. Thermal stresses are induced when packages containing materials with differing coefficients of thermal expansion are heated, and cure stresses are induced as thermosetting polymer materials shrink during the cure process. These stresses are developed during processing and remain as residual stresses within the component after the manufacturing process is complete. As residual stresses will directly affect the reliability of the device, it is necessary to assess their magnitude and the effect on package reliability. A coupled multiphysics model has been developed to numercially analyse the microwave curing process. In order to obtain a usefully accurate model of this process, a holistic approach has been taken, in which the process is not considered to be a sequence of discrete steps, but as a complex coupled system. An overview of the implemented numerical model is presented, with particular focus paid to analysis of induced thermal stresses. Results showing distribution of stresses within an idealised microelectronics package are presented and discussed.