Using a MILP model to establish a framework for an annualised hours agreement

Production flexibility is essential for industrial companies that have to deal with seasonal demand. Human resources are one of the main sources of flexibility. Annualising working hours (i.e., the possibility of irregularly distributing the total number of working hours over the course of a year) is a tool that provides flexibility to organizations; it enables a firm to adapt production capacity to fluctuations in demand. However, it can imply a worsening of the staff’s working conditions. To take the human aspect into account, the planning and scheduling of working time should comply with constraints derived from the law or from a collective bargaining agreement. Furthermore, new and more difficult working-time planning and scheduling problems are arising. This paper proposes a mixed-integer linear program model to solve the problem of planning the production and the working hours of a human team that operates in a multi-product process. Solving the model for different settings provides the essential quantitative information to negotiate the best conditions of the annualised hours system (the elements to establish the trade-off between weekly flexibility and economic or working-time reduction compensation can be obtained). The results achieved in a computational experiment were very satisfactory.     

Planning production and working time within an annualised hours scheme framework

Production flexibility is essential for industrial companies that have to deal with seasonal demand. Human resources are one of the main sources of flexibility. Annualising working hours (i.e., the possibility of irregularly distributing the total number of working hours over the course of a year) is a tool that provides organisations with flexibility; it enables a firm to adapt production capacity to fluctuations in demand. However, it can involve a worsening of the staff working conditions. To take this into account, the planning and scheduling of working time should comply with constraints derived from the law or from a collective bargaining agreement. Thus, new and more difficult working-time and production planning and scheduling problems are arising. This paper proposes two mixed-integer linear program models for solving the problem of planning the production, the working hours and the holiday weeks of the members of a human team operating in a multi-product process in which products are perishable, demand can be deferred and temporary workers are hired to stand in for employees. The results of a computational experiment are presented. Supported by the Spanish MCyT projects DPI2001-2176 and DPI2004-05797, co-financed by FEDER.     

Insights into CO/styrene copolymerization by using Pd(II) catalysts containing modular pyridine-imidazoline ligands

Continuing our studies into the effect that N-N' ligands have on CO/styrene copolymerization, we prepared new C(1)-symmetrical pyridine-imidazoline ligands with 4',5'-cis stereochemistry in the imidazoline ring (5) and 4',5'-trans stereochemistry (6-10) and compared them with our previously reported ligands (1-4). Their coordination to neutral methylpalladium(II) (5 a-10 a) and cationic complexes (5 b-10 b), investigated in solution by NMR spectroscopy, indicates that both the electronic and steric properties of the imidazolines determine the stereochemistry of the palladium complexes. The crystal structures of two neutral palladium precursors [Pd(Me)(2-n)Cl(n)(N-N')] (n=1 for 8 a; n=2 for 9 a') show that the Pd-N coordination distances and the geometrical distortions in the imidazoline ring depend on the electronic nature of the substituents in the imidazoline fragment. Density functional calculations performed on selected neutral and cationic palladium complexes compare well with NMR and X-ray data. The calculations also account for the formation of only one or two stereoisomers of the cationic complexes. The performance of the cationic complexes as catalyst precursors in CO/4-tert-butylstyrene copolymerization under mild pressures and temperatures was analyzed in terms of the productivity and degree of stereoregularity of the polyketones obtained. Insertion of CO into the Pd-Me bond, which was monitored by multinuclear NMR spectroscopy, shows that the N ligand influences the stereochemistry of the acyl species formed.     

The reverse self-dual serial cost-sharing rule

In this study we define a cost-sharing rule for cost-sharing problems. This rule is related to the serial cost-sharing rule defined by Moulin and Shenker (Econometrica 60:1009–1037, 1992). We give some formulas and axiomatic characterizations for the new rule. The axiomatic characterizations are related to some previous ones provided by Moulin and Shenker (J. Econ. Theory 64:178–201, 1994) and Albizuri (Theory Decis. 69:555–567, 2010).     

Levels of polycyclic aromatic hydrocarbons,polychlorinated byphenyls,methylmercury and butyltins in the natural UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay,Spain)

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), methylmercury (MeHg⁺) and butyltins (mono-, di- and tri-butyltin, MBT, DBT and TBT) were monitored in oysters (Crassostrea sp.) and sediments collected in different sampling points of the UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay) from March 2006 to June 2007. In the case of oyster samples, concentrations in the 290–1814 µg kg^?1 (PAHs), 70–475 µg kg^?1 (PCBs), 75–644 µg kg^?1 (MeHg⁺) and 200–1300 µg kg^?1 (as a sum of the three butyltins) ranges were obtained. In most samples TBT was the most abundant butyltin, followed by DBT and MBT. It should be highlighted that most samples exceeded the highest range (367 µg kg^?1) found in the last mussel watch programme carried out by the National Oceanic and Atmospheric Administration (NOAA) for butyltins in oyster samples. This could be due to the presence of a shipyard in the estuary. Sediment concentrations ranged as follows: total PAHs (856–3495 µg kg^?1) and total PCBs (58–220 µg kg^?1). Organometallic species were always below the limits of detection (LODs) (0.24 µg kg^?1 for MeHg⁺, 0.6 µg kg^?1 for MBT, 0.48 µg kg^?1 for DBT and 1.1 µg kg^?1 for TBT). In both sediment and oyster PAH sources were mostly combustion. In the case of PCBs, 4-6 chlorine-atom congeners were the most abundant ones. Slight differences in the profile of PAHs as well as PCBs can be detected when the matrices were compared with each other. Finally, in the case of PAHs, sediment and water column played the main role in the accumulation pathway into the organisms in all the sampling stations.     

A detailed workforce planning model including non-linear dependence of capacity on the size of the staff and cash management

This paper introduces an original planning model which integrates production, human resources and cash management decisions, taking into account the consequences that decisions in one area may have on other areas and allowing all these areas to be coordinated. The most relevant characteristics of the planning problem are: (1) production capacity is a non-linear function of the size of the staff; (2) firing costs may depend on the worker who is fired; (3) working time is managed under a working time account (WTA) scheme, so positive balances must be paid to workers who leave the company; (4) there is a learning period for hired workers; and (5) cash management is included. A mixed integer linear program is designed to solve the problem. Despite the size and complexity of the model, it can be solved in a reasonable time. A numerical example, the main results of a computational experiment and a sensibility analysis illustrate the performance and benefits of the model.     

Plasticization and cocrystallization in LLDPE/wax blends

The structure and thermal properties of linear low‐density polyethylene (LLDPE)/medium soft paraffin wax blends, prepared by melt mixing, were investigated by differential scanning calorimetry (DSC) and small‐ and wide‐angle X‐ray scattering (SAXS and WAXS). The blends form a single phase in the melt as determined by SAXS. Upon cooling from the melt, two crystalline phases develop for blends with more than 10 wt % wax characterized by widely different melting points. The wax acts as an effective plasticizer for LLDPE, decreasing both its crystallization and melting temperature. The higher melting point crystalline phase is formed by less branched LLDPE fractions. On the other hand, the lower melting point crystalline phase is a wax‐rich phase constituted by cocrystals of extended chain wax and short linear sequences of highly branched LLDPE chains. The presence of cocrystals was evidenced by standard DSC results, successive self‐nucleation and annealing (SSA) thermal fractionation and by the detection of a new SAXS signal attributed to the lamellar long period of the cocrystals. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1469–1482     

Progress on the development of uniform distributed Pd electroless based catalysts on MEA for PEMFC application

Envisaging the scale-up production of fuel cell electrodes, it was established an electrode manufacturing method that enables a uniform distribution of Pd-based catalyst over the MEA, ensuring simultaneously a low catalyst loading. The new procedure relies on the direct immobilization of the catalyst on the gas diffusion substrate by the electroless deposition after substrate activation by the electrodeposition of metal nucleus of Pd using the galvanostatic mode. The effect of the novel method on the catalyst distribution uniformity, morphology, and electrocatalytic activity towards the oxygen reduction reaction (ORR) in 0.1 M HClO₄ solution is compared to samples prepared by the conventional Sn/Pd sensitization—activation route. The performance of the PEMFC containing the same Pd load (0.09 mg cm^?2) reveals to be slightly higher on depositing the Pd nucleus by the galvanostatic electrodeposition than by the conventional sensitization/activation method. The new method opens up new approaches to extend the electroless deposition to the preparation of a wide range of alloy catalysts for the cathode and anode sides of PEMFCs.     

Synthesis and Characterization of a Novel Addition-Fragmentation Reactive Surfactant (TRANSURF) for Use in Free-Radical Emulsion Polymerizations

The synthesis and characterization of a new type of chain-transfer-active surfactant (i.e., TRANSURF) is reported. The compound was designed on the basis of the chemistry of macromers, which undergo free-radical chain-transfer addition-fragmentation reactions. In effect this allows incorporation of the surfactant molecule into the polymer backbone, and thus reduces the influence of surfactant migration during film formation. Surfactants of this type, containing two hydrophilic head groups, can have a marked influence on the polymer and latex properties (e.g., molecular weight distributions and particle size). Characterization of the physical properties of this surfactant was therefore carried out using surface tension, conductivity, and fluorescence techniques. Because of the surfactant's unusual "bolaform" (alpha, omega) (Zana, R., in "Structure-Performance Relationships in Surfactants" (K. Esumi and M. Ueno, Eds.), Surfactant Science Series 70, Dekker, New York, 1997) structure the micelle formation process has been found to be quite different from that of the conventional surfactant, sodium dodecyl sulfate (SDS). From the surface tension data a flat molecular conformation was evident at 1x10(-3) mol dm(-3) (131 ?(2) surface area), which we assumed to correspond to the low aggregation number of premicellar aggregates. There is evidence to suggest formation of a larger volume of the microdomains in these micelles compared to that in SDS. At higher TRANSURF concentrations, however, we find no clear indication of a switch to a "wicket"-type conformation, although such conformational changes cannot be ruled out. Copyright 2001 Academic Press.     

Effect of the conformation of the alkyl chain on the catalytic miniemulsion copolymerization of ethylene and acrylates

The catalytic copolymerization of ethylene and acrylic monomers is a promising way of incorporating polar functionality into polyolefins and therefore enlarging the range of properties of these materials. This work shows that for the copolymerization of ethylene and C4 acrylates using a sterically encumbered Pd catalyst, the degree of incorporation of the acrylic monomer decreases with the degree of branching of the alkyl chain of the acrylate, the main reason being the difficulty for coordination of bulky acrylates to the catalytic site. This strongly affects the polymerization rate as well as the molecular weight, crystallinity and melting point temperature of the copolymers.