Optimization‐based framework for computer‐aided molecular design

A new framework to automate, augment, and accelerate steps in computer‐aided molecular design is presented. The problem is tackled in three stages: (1) composition design, (2) structure determination, and (3) extended design. Composition identification and structure determination are decoupled to achieve computational efficiency. Using approximate group‐contribution methods in the first stage, molecular compositions that fit design targets are identified. In the second stage, isomer structures of solution compositions are determined systematically, and structure‐based property corrections are used to refine the solution pool. In the final stage, the design is extended beyond the scope of group‐contribution methods by using problem‐specific property models. At each design stage, novel optimization models and graph theoretic algorithms generate a large and diverse pool of candidates using an assortment of property models. The wide applicability and computational efficiency of the proposed methodology are illustrated through three case studies. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3686–3701, 2013     

Colorimetric characterization of a computer‐controlled liquid crystal display

A new method was used to characterize computer‐controlled liquid crystal displays (LCDs). The characterization, which was performed to enable colorimetric image display, included channel independence, spatial independence, screen uniformity, and colorimetry. The colorimetric model consisted of three one‐dimensional look‐up tables (LUTs) describing each channel's optoelectronic transfer function and a 3 × 4 matrix transformation that included black‐level flare. The matrix coefficients were estimated statistically by minimizing the average CIEDE2000 color difference for a data set sampling the display's colorimetric gamut. The LUTs were recreated dynamically throughout the optimization of the matrix coefficients. The characterization was implemented with three different instruments to evaluate the robustness of the method with respect to measurement uncertainty. The average performance ranged between 0.1 and 0.4 ΔE₀₀ and was well correlated with instrument precision. The optimization approach improved performance by a factor of two compared with direct measurements. Despite differences in instrument design, the chromaticities of each primary following optimization and black‐level flare compensation were very similar. This excellent performance was a result of the display's optoelectronic properties well matching the model assumptions. The technique was also used to characterize three additional LCD displays ranging in their matching of the model assumptions. In this case, performance worsened. For one display, more complex models would be required for colorimetric characterization. Finally, a colorimetric characterization based on measurements at the center of the display and perpendicular to the face was used to predict measurements at the edges and at different angles. The results indicated that characterizations would be required at multiple positions and angles in order to achieve sufficient accuracy. © 2004 Wiley Periodicals, Inc. Col Res Appl, 29, 365–373, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.20046     

Computer‐aided design of tailor‐made ionic liquids

Ionic liquids (IL), with their negligible vapor pressure, have the potential to replace volatile organic solvents in several processes. They also exhibit other unique characteristics, such as high thermal stability, wide liquid range, and wide electrochemical window, which make them attractive for many important applications. In addition, millions of ILs can be formed through different combination of cations, anions, and other functional groups. Till now, majority of work on IL selection, for a given application, is guided by trial and error experimentation. In this article, we present a computer‐aided IL design framework, based on semiempirical structure‐property models and optimization methods, which can consider several IL candidates and design optimal structures for a given application. This powerful methodology has great potential to act as a knowledge‐based framework to aid synthetic chemists and engineers develop new ILs. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4627–4640, 2013     

Improvement of mechanical properties of polycaprolactone scaffolds by applying piezoelectric vibration system based on a dispensing process: A new concept

The mechanical properties of biomedical scaffolds are important for applications in tissue regeneration. The dispensing system described herein, which is based on a solid free‐form fabrication technique, enables the production of design‐based scaffolds with controllable pore structures. Although current plotting systems can easily fabricate a variety of three‐dimensional scaffolds, the mechanical properties of these constructs are difficult to control because of low processing speed. To overcome this limitation, a new dispensing method, which uses a piezoelectric vibration system to improve mechanical properties, has been developed. Polycaprolactone (PCL) strands fabricated using this technique were roughly 70% stronger than normal PCL strands. To explain this increase in mechanical strength, the combined effects of the piezoelectric system and the melt‐dispensing process on the crystalline morphology and molecular orientation of PCL strands were investigated. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

An integrated qualitative and quantitative modeling framework for computer‐assisted HAZOP studies

The article proposes a novel practical framework for computer‐assisted hazard and operability (HAZOP) that integrates qualitative reasoning about system function with quantitative dynamic simulation in order to facilitate detailed specific HAZOP analysis. The practical framework is demonstrated and validated on a case study concerning a three‐phase separation process. The multilevel flow modeling (MFM) methodology is used to represent the plant goals and functions. First, means‐end analysis is used to identify and formulate the intention of the process design in terms of components, functions, objectives, and goals on different abstraction levels. Based on this abstraction, qualitative functional models are constructed for the process. Next MFM‐specified causal rules are extended with systems specific features to enable proper reasoning. Finally, systematic HAZOP analysis is performed to identify safety critical operations, its causes and consequences. The outcome is a qualitative hazard analysis of selected process deviations from normal operations and their consequences as input to a traditional HAZOP table. The list of unacceptable high risk deviations identified by the qualitative HAZOP analysis is used as input for rigorous analysis and evaluation by the quantitative analysis part of the framework. To this end, dynamic first‐principles modeling is used to simulate the system behavior and thereby complement the results of the qualitative analysis part. The practical framework for computer‐assisted HAZOP studies introduced in this article allows the HAZOP team to devote more attention to high consequence hazards. © 2014 American Institute of Chemical Engineers AIChE J 60: 4150–4173, 2014     

3D printing hybrid organometallic polymer‐based biomaterials via laser two‐photon polymerization

Materials with microscale structures are gaining increasing interest due to their range of technical and medical applications. Additive manufacturing approaches to such objects via laser two‐photon polymerization, also known as multiphoton fabrication, enable the creation of new materials with diverse and tunable properties. Here, we investigate the properties of 3D structures composed of organometallic polymers incorporating aluminium, titanium, vanadium and zirconium. The organometallic polymer‐based materials were analysed using a variety of techniques including SEM, energy‐dispersive X‐ray spectroscopy, X‐ray photoelectron spectroscopy analysis and contact angle measurements and their biocompatibility was tested in vitro. Cell viability and mode of death were determined by 3‐(4,5‐dimethyl‐2‐thiazolyl)‐2,5‐diphenyl‐2H‐tetrazolium bromide (MTT) assay and acridine orange/ethidium bromide staining. Polymers incorporating Al, Ti and Zr supported cell adhesion and proliferation, and showed low toxicity in vitro, whereas the organometallic polymer incorporating V was shown to be cytotoxic. Inductively coupled plasma optical emission spectrometry suggested that leaching of the V from the organometallic polymer is the likely cause of this. The preparation of the organometallic polymers is straightforward and both simple 2D and complex 3D structures can be fabricated with ease. Resolution tests of the newly developed organometallic polymer incorporating Al show that suspended lines with widths down to 200 nm can be fabricated. We believe that the materials described in this work show promising properties for the development of objects with sub‐micron features for biomedical applications (e.g. biosensors, drug delivery devices, tissue scaffolds etc.). © 2019 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Estimating black‐level emissions of computer‐controlled displays

It is quite common for computer‐controlled displays to emit light in image areas set to digital values of zero, referred to as their black level. This is expected for liquid–crystal displays and also can occur for cathode‐ray tube displays when the “brightness” (gun‐amplifier offset) is set excessively high. For either display, the light emission at the black level results in color channels whose chromaticities vary with luminance level. Consequently, typical methods of colorimetric characterization result in large error. When this black‐level emission is measured and accounted for suitably, characterization accuracy is dramatically improved. Unfortunately, many instruments used to measure displays have too low a sensitivity to measure black‐level emission with sufficient precision and accuracy. A method of estimating black‐level emissions was derived and tested. Because the optimal black‐level results in channel chromaticities that are invariant to the greatest extent with luminance level, an objective function was defined as the sum of chromaticity variances of each channel over a range of measurements. Minimizing this objective function resulted is an estimate of a display's black level. The estimated black level resulted in equivalent or superior performance to direct measurements. © 2003 Wiley Periodicals, Inc. Col Res Appl, 28, 379–383, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.10181     

Synthesis from Molecule into 3D Polyamide 6 Microspheres Stacked Polyhedrons via Self‐Assembly

Self‐assembly provides the basis for a procedure used to organize larger objects into regular, 3D microsphere stacked polyhedrons. A novel approach is described for the fabrication of 3D structured micrometer‐scale polyhedrons which are packed with nanosized spheres in the order of 400 nm by in situ polymerization using phase inversion technology. The extended polyhedrons can assemble into decimeter‐level ordered materials. The side length of an individual polyhedron can be effectively tuned from 10 to 100 µm through several ways. This method realizes directly self‐assembly from molecule to regular extended polyhedrons materials. The process is primarily based on in situ anion polymerization of lactam in two‐phase system whose self‐assembly is driven by hydrogen bonds' force and polyethylene glycol stepwise crystallization synergistically. The results suggest that this strategy for self‐assembly can be applied to design nonplanar complex geometric structure materials. In the future, polyhedrons packed with microspheres may be possible to build more complex 3D, self‐assembly device modules for advanced materials.     

Optimal design and manufacture of thin‐walled polystyrene structures

In this study, we investigated the implementation of an automatic procedure for optimizing thermoformed thin‐walled structures. Such objects are created in great numbers, especially in the food packaging industry. The methodology for the optimal design of such structures is based on the use of a parameterized geometry model created within an interactive design environment. By varying the parameters associated with the computer‐aided design (CAD) model, one can create a rich variety of possible designs. One can then subject these designs to physical analysis to calculate their physical properties, and thus select an optimal design. The two distinct stages of this process—the prediction of the shape of the thermoformed structure, and the physical behavior of the structure—were validated by experiments. This article reports the experimental investigation of the deformation behavior of polystyrene, the mechanical behavior of specially prepared deformed polystyrene sheets, and the response to loading of a hemispherical structure (used in the validation). POLYM. ENG. SCI., 45:694–703, 2005. © 2005 Society of Plastics Engineers     

Outer approximation algorithm with physical domain reduction for computer‐aided molecular and separation process design

Integrated approaches to the design of separation systems based on computer‐aided molecular and process design (CAMPD) can yield an optimal solvent structure and process conditions. The underlying design problem, however, is a challenging mixed integer nonlinear problem, prone to convergence failure as a result of the strong and nonlinear interactions between solvent and process. To facilitate the solution of this problem, a modified outer‐approximation (OA) algorithm is proposed. Tests that remove infeasible regions from both the process and molecular domains are embedded within the OA framework. Four tests are developed to remove subdomains where constraints on phase behavior that are implicit in process models or explicit process (design) constraints are violated. The algorithm is applied to three case studies relating to the separation of methane and carbon dioxide at high pressure. The process model is highly nonlinear, and includes mass and energy balances as well as phase equilibrium relations and physical property models based on a group‐contribution version of the statistical associating fluid theory (SAFT‐γ Mie) and on the GC⁺ group contribution method for some pure component properties. A fully automated implementation of the proposed approach is found to converge successfully to a local solution in 30 problem instances. The results highlight the extent to which optimal solvent and process conditions are interrelated and dependent on process specifications and constraints. The robustness of the CAMPD algorithm makes it possible to adopt higher‐fidelity nonlinear models in molecular and process design. © 2016 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 62: 3484–3504, 2016     

Study of Air‐Liquid Flow Patterns in Hydrocyclone Enhanced by Air Bubbles

In order to improve the oil‐water separation efficiency of a hydrocyclone, a new process utilizing air bubbles has been developed to enhance separation performance. Using the two‐component phase Doppler particle analyzer (PDPA) technique, the velocities of two phases, air and liquid, and air bubble diameter were measured in a hydrocyclone. The air‐liquid mixing pump can produce 15 to 60 μm‐diameter air bubbles in water. There is an optimum air‐liquid ratio for oil‐water separation of a hydrocyclone enhanced by air bubbles. An air core occurs in the hydrocyclone when the air‐liquid ratio is more than 1 %. The velocities of air bubbles have a similar flow pattern to the water phase. The axial and tangential velocity differences of the air bubbles at different air‐liquid ratio are greater near the wall and near the core of the hydrocyclone. The measured results show that the size distribution of the air bubbles produced by the air‐liquid mixing pump is beneficial to the process where air bubbles capture oil droplets in the hydrocyclone. These studies are helpful to understand the separation mechanism of a hydrocyclone enhanced by air bubbles.     

COSMO‐based computer‐aided molecular/mixture design: A focus on reaction solvents

In this article, we investigate reaction solvent design using COSMO‐RS thermodynamics in conjunction with computer‐aided molecular design (CAMD) techniques. CAMD using COSMO‐RS has the distinct advantage of being a method based in quantum chemistry, which allows for the incorporation of quantum‐level information about transition states, reactive intermediates, and other important species directly into CAMD problems. This work encompasses three main additions to our previous framework for solvent design (Austin et al., Chem Eng Sci. 2017;159:93–105): (1) altering the group contribution method to estimate hydrogen‐bonding and non‐hydrogen‐bonding σ‐profiles; (2) ab initio modeling of strong solute/solvent interactions such as H‐bonding or coordinate bonding; and (3) solving mixture design problems limited to common laboratory and industrial solvents. We apply this methodology to three diverse case studies: accelerating the reaction rate of a Menschutkin reaction, controlling the chemoselectivity of a lithiation reaction, and controlling the chemoselectivity of a nucleophilic aromatic substitution reaction. We report improved solvents/mixtures in all cases. © 2017 American Institute of Chemical Engineers AIChE J, 63: 104–122, 2018     

Mechanical Assembly of Thermo‐Responsive Polymer‐Based Untethered Shape‐Morphing Structures

Shape‐morphing robotic structures can provide innovative approaches for various applications ranging from soft robotics to flexible electronics. However, the programmed deformation of direct‐3D printed polymer‐based structures cannot be separated from their subsequent conventional shape‐programming process. This work aims to simplify the fabrication process and demonstrates a rapid and adaptable approach for building stimulus‐responsive polymer‐based shape‐morphing structures of any shape. This is accomplished through mechanically assembling a set of identical self‐bending units in different patterns to form morphing structures using auxiliary hard connectors. A self‐bending unit fabricated by a 3D printing method can be actuated upon heating without the need for tethered power sources and is able to transform from a flat shape to a bending shape. This enables the assembled morphing‐structure to achieve the programmed integral shape without the need for a shape‐programming process. Differently assembled morphing structures used as independent robotic mechanisms are sequentially demonstrated with applications in biomimetic morphing structures, grasping mechanisms, and responsive electrical devices. This proposed approach based on a mechanical assembling method paves the way for rapid and simple prototyping of stimulus‐responsive polymer‐based shape‐morphing structures with arbitrary architectures for a variety of applications in deployable structures, bionic mechanisms, robotics, and flexible electronics.     

Role of Collective Interactions in Self‐Assembly of Charged Particles at Liquid Interfaces

Charged nano‐colloidal particles self‐assemble and display ordered arrays or other structures at liquid interfaces. We used Monte Carlo (MC) simulations to examine the effect of long‐range repulsive collective inter‐particle interactions on structural—transitions from liquid‐like to crystal‐like. We used the asymptotic pair interaction potential proposed by Hurd (J. Phys. A. Math Gen 18 , L1055 (1985)), which includes both the screened Coulombic contribution and the dipole‐dipole interaction. The effects of the collective inter‐particle interactions on the interfacial 2‐D colloid structure formation were quantified by the radial distribution function and the potential of the mean force. The MC simulations agreed with the experimentally observed particle structural transitions at both the air‐water and oil‐water interfaces. The effects of the particle charge and interfacial coverage on the 2‐D structure formation were analyzed. The significance of the results lies in their potential applications in inducing 2‐D structural transitions in interfacial colloids to form ordered structures; this controls the emulsion and foam stability, and aids in the fabrication of patterned materials with desirable properties.     

Unique block molecules based on glycerol skeleton as C‐3 building blocks for liquid crystals formation by self‐assembly and their future potential for the “nano‐chemistry”

Studies on design of liquid crystalline block molecules with non‐conventional mesophase morphoplogies have been proposed by Tschierske and co‐workers. These block molecules have a rigid core, a lateral substituent, and an alkyl chain segmenting blocks from each other. Related to this, diglyceryl alkyl ethers found by us have glycerol as a rigid core, a lateral substituent, and an alkyl chain similar to the Tschierske design. These two cases are compared with each other with regard to the relationship between the molecular structure and the liquid crystalline morphologies and other properties. Recently, new soft materials suitable for liquid crystals exhibiting self‐assembly of phase‐segregated structures have been designed. Typical examples of such “block” molecules containing glycerol having a C‐3 building block include: (i) undecyl‐glycerylether‐ modified siloxane derivatives with a siloxane segment as the rigid core and alkyl chains with 2, 3‐dihydroxypropoxy group as a hydrophilic group at a lateral or terminal position of the siloxane segment; (ii) novel hyper branched dendrimers forming the basis of polyglycerol nanocapsules with a core‐shell molecular architecture; (iii) carbon nanotubes based on cyclodextrins (CDs); (iv) polymerizable amphiphilic diacetylene‐containing phospholipids suitable for construction of functional nanocomposites. This is done by self‐assembly and polymerization of diacetylene creating a “block molecular structure” with a polyacetylene chain as a rigid core segment, the lipid headgroups as the hydrophilic segment, and terminal flexible alkyl chains. On the basis of these results, future potential of block molecules as a soft building material for liquid crystalline structures was discussed.     

The Critical Energy of Direct Initiation in Liquid Fuel‐Air and Liquid Fuel‐RDX Powder‐Air Mixtures in a Vertical Detonation Tube

Multiphase cloud detonation is an important but complex process, which has not been fully understood yet. Direct experimental data about the critical initiation energy (CIE) and pressure/velocity revolution of high explosive powder‐based multiphase cloud detonation is not available in the literature. In this paper, propylene oxide (PO), petroleum ether (PE), isopropyl nitrate (IPN), and a mixture of PE/IPN were individually dispersed to form a cloud in a 200 mm×5400 mm vertical detonation tube. Subsequently, this cloud was directly ignited by a high explosive. The critical initiation energy of various mist/air mixtures was measured by the up and down method. Meanwhile, the pressure history was recorded by six sensors along the detonation tube. RDX powder was added to the system and sprayed simultaneously with the liquid fuel to form a three‐phase gas‐liquid‐solid explosive cloud. The detonation pressure and velocity of all three‐phase cases significantly increased while the corresponding critical initiation energy decreased compared to the liquid‐air analogs. The CIE data were found to have a “U”‐shaped curve relationship to the fuel‐air ratio in two‐ and three‐phase systems, the minimum is always on the fuel‐rich side.     

Impact Optimization of 3D‐Printed Poly(methyl methacrylate) for Cranial Implants

Material extrusion‐based additive manufacturing, also known as fused filament fabrication (FFF) or 3D printing facilitates the fabrication of cranial implants with different materials and complex internal structures. The impact behavior plays a key role in the designing process of cranial implants. Therefore, the performance of impact tests on novel implant materials is of utmost importance. This research focuses on investigating the dependency of the infill density and pattern on the impact properties of 3D‐printed poly(methyl methacrylate) (PMMA) sandwich specimens including internal rectilinear, gyroid, and 3D‐honeycomb (3D‐HC) structures. 3D‐HC structures show higher impact forces and dissipated energies as well as dynamic stiffness values compared to rectilinear and gyroid structures at the same infill density. 70% infill 3D‐HC and 100% infill rectilinear structures prove to be most promising. In addition, two different optimization techniques to further improve the impact properties of these specimens, namely a material and a topology optimization, are applied. Topology optimization shows promising results until first damage and material optimization regarding dissipated energies. However, both are not able to outperform the 3D‐HC pattern.     

CFD‐assisted Characterization and Optimization of the Structured Mass Transfer Packing QVF DURAPACK®

The glass packing QVF DURAPACK® was developed to use the advantages of structured mass transfer packings, especially when handling corrosive media. To match up with the latest developments for sheet metal packings, further optimization for liquid‐liquid separation processes was performed for the QVF DURAPACK®. The complex geometry of structured packings and the wall thickness of glass sheets complicate the numerical investigations. The modeling strategy is presented, and the limitations of CFD tools are given. The experimental and numerical results show similar trends as known for perforated metal structures. The extraction efficiency of the packing prototype could also be reproduced with the column design tool LLECMOD.     

Optimization‐driven design of dies for profile extrusion: Parameterization,strategy, and performance

A computational design optimization environment is developed, handling, for the first time, streamline dies used for profiles in unplasticized polyvinyl chloride (uPVC) having multiple complex features, as well as simpler designs. Die cavity cross sections are described by planar contours, such as the cutting paths for wire electrical discharge machining of the plates from which streamline profile dies are constructed. Contours are parameterized using key points, and by joining the contours with ruled surfaces, the three‐dimensional geometry can be reconstructed. For the optimization a developed flow analysis on each die cross section is used with the avoid‐cross‐flow strategy. Cross sections are partitioned and the die is balanced to obtain the required flow rate through each. A robust and efficient parallel decoupled optimization strategy is developed. In application to a uPVC window profile, five cross sections were optimized. The number of design variables on each ranged from 2 to 46, and the cross section optimizations converged within one to seven cycles. Compared with the work of an experienced designer making manual changes to the computer‐aided design model, guided by computational fluid dynamics analyses, the design quality was comparable or better and computational demands similar; however, the time required from the designer was reduced seven times. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

UV curing-assisted 3D plotting of ceramic feedstock containing thermo-regulated phase-separable,photocurable vehicle for dual-scale porosity structure

We propose a novel approach for manufacturing dual-scale porosity alumina structures by UV curing-assisted 3D plotting of a specially formulated alumina feedstock using a thermo-regulated phase separable, photocurable camphene/triethylene glycol dimethacrylate (TEGDMA) vehicle. In particular, 3D plotting process was conducted at - 5 °C, and thus an alumina suspension prepared using liquid camphene/TEGDMA at room temperature could undergo phase separation, resulting in camphene crystals surrounded by walls comprised of liquid photopolymer enclosing alumina particles. To enhance the shape retention ability of extruded filaments, polystyrene (PS) polymer was used as the tackifier. The phase-separated feedrod could be extruded favorably through a nozzle and rapidly photopolymerized by UV light during the 3D plotting process. Three-dimensionally interconnected macropores were tightly constructed, which were separated by microporous alumina filaments, where micropores were created by the removal of camphene crystals via freeze-dying. The macroporosity of porous alumina ceramics was controlled by adjusting the distance between deposited filaments, while their microporosity was kept constant, leading to tightly tailored overall porosity and mechanical properties.