Packing Compaction Research Articles

Selection Results of Solid Material for Horizontal and Highly-Deviated Well Completion Gravel-Packing: Experiments, Numerical Simulation and Proposal

Lightweight and ultra-lightweight solid materials are being used in gravel packing for horizontal wells instead of traditional quartz and ceramsite to decrease the risk of premature plugging and improve packing efficiency. Physical and numerical simulation experiments of gravel packing were conducted to assess the effectiveness of reducing solid material density and investigate its impact on packing and sand control. Packed gravel destabilization experiments highlighted the importance of high-compaction degree packing for effective sand control. Further gravel packing experiments examined the packing performance of different solid materials, revealing that lightweight solids have minimal gravitational deposition effect because their density is similar to the gravel slurry, relying primarily on fluid flow for compaction. The numerical simulation indicated that lightweight ceramsite is unsuitable for horizontal and highly-deviated wells because of its poor compaction degree and sand control, especially with high-viscosity slurry. High-density particles enhance gravitational deposition, improving packing compaction and sand control. Lightweight materials are recommended only when advanced plugging of α wave packing cannot be avoided. In highly-deviated wells, high-density materials significantly improve packing stability and sand control. This study provides clear technical guidelines for selecting solid materials for gravel packing in horizontal and highly-deviated wells.

Computer Vision Method for Automatic Detection of Microstructure Defects of Concrete.

The search for structural and microstructural defects using simple human vision is associated with significant errors in determining voids, large pores, and violations of the integrity and compactness of particle packing in the micro- and macrostructure of concrete. Computer vision methods, in particular convolutional neural networks, have proven to be reliable tools for the automatic detection of defects during visual inspection of building structures. The study's objective is to create and compare computer vision algorithms that use convolutional neural networks to identify and analyze damaged sections in concrete samples from different structures. Networks of the following architectures were selected for operation: U-Net, LinkNet, and PSPNet. The analyzed images are photos of concrete samples obtained by laboratory tests to assess the quality in terms of the defection of the integrity and compactness of the structure. During the implementation process, changes in quality metrics such as macro-averaged precision, recall, and F1-score, as well as IoU (Jaccard coefficient) and accuracy, were monitored. The best metrics were demonstrated by the U-Net model, supplemented by the cellular automaton algorithm: precision = 0.91, recall = 0.90, F1 = 0.91, IoU = 0.84, and accuracy = 0.90. The developed segmentation algorithms are universal and show a high quality in highlighting areas of interest under any shooting conditions and different volumes of defective zones, regardless of their localization. The automatization of the process of calculating the damage area and a recommendation in the "critical/uncritical" format can be used to assess the condition of concrete of various types of structures, adjust the formulation, and change the technological parameters of production.

Effect of ceramic waste tile as a fine aggregate on the mechanical properties of low-carbon ultrahigh performance concrete

Overmining of sand from natural resources has seriously impacted the environment, hindering the sustainable development of concrete. Ceramic waste tile has a chemical component similar to that of sand and can be a potentially excellent substitute for sand. Therefore, this study uses 20 %, 40 %, 60 %, 80 %, and 100 % ceramic waste tile aggregate (CTWA) to replace sand in equal amounts to produce low-carbon ultrahigh performance concrete (UHPC). The workability and mechanical properties of UHPC with varying CTWA content is explored. Additionally, the interface transition area (ITZ) and pore structure of UHPC are characterized by scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP), respectively. Finally, the modified Andersen and Andresen (MAA) model is employed to evaluate the effect of CTWA on the UHPC packing compactness. The results show that the incorporation of CTWA reduces the flowability of UHPC. However, the spread flow for UHPC with 100 % CTWA can also reach a value of 398 mm. The UHPC with 100 % CTWA exhibits better mechanical properties, as reflected by an improvement in compressive strength and flexural strength of 15.5 % and 26.5 %, respectively, at a curing age of 28 d. Moreover, the addition of CTWA shows no significant negative effect on the fracture toughness of UHPC. Microstructure analysis demonstrates that the ITZ and pore structure of UHPC with CTWA are effectively improved due to the internal curing and better particle gradation of CTWA. Therefore, CTWA, with economic and environmental advantages, is a practicable alternative fine aggregate for UHPC.

Capacitive energy storage from single pore to porous electrode identified by frequency response analysis

Rate capability, peak power, and energy density are of vital importance for the capacitive energy storage (CES) of electrochemical energy devices. The frequency response analysis (FRA) is regarded as an efficient tool in studying the CES. In the present work, a bi-scale impedance transmission line model (TLM) is firstly developed for a single pore to a porous electrode. Not only the TLM of the single pore is re-parameterized but also the particle packing compactness is defined in the bi-scale. Subsequently, the CES properties are identified by FRA, focused on rate capability vs. characteristic frequency, peak power vs. equivalent series resistance, and energy density vs. low frequency limiting capacitance for a single pore to a porous electrode. Based on these relationships, the CES properties are numerically simulated and theoretically predicted for a single pore to a porous electrode in terms of intra-particle pore length, intra-particle pore diameter, inter-particle pore diameter, electrolyte conductivity, interfacial capacitance & exponent factor, electrode thickness, electrode apparent surface area, and particle packing compactness. Finally, the experimental diagnosis of four supercapacitors (SCs) with different electrode thicknesses is conducted for validating the bi-scale TLM and gaining an insight into the CES properties for a porous electrode to a single pore. The calculating results suggest, to some extent, the inter-particle pore plays a more critical role than the intra-particle pore in the CES properties such as the rate capability and the peak power density for a single pore to a porous electrode. Hence, in order to design a better porous electrode, more attention should be given to the inter-particle pore.

Investigation of steel fiber reinforced high-performance concrete with full aeolian sand: Mix design, characteristics and microstructure

High-performance concrete with full aeolian sand (FA-HPC) has the characteristics of low water binder ratio, large cementitious materials content and no restriction of coarse aggregates, resulting in a high risk of shrinkage cracking. Aiming at reducing the shrinkage of FA-HPC and improving its cracking resistance, mechanical properties and durability, steel fibers with different lengths are employed to reinforce FA-HPC and develop a new type of cement-based composites (FA-HPFRC). For this purpose, the modified Andreasen & Andersen (MAA) model was adopted to determine the volume fractions of aeolian sand (AS), cement, fly ash (FA) and silica fume (SF). Then, the water binder ratio (W/C), superplasticizer (SP) and steel fiber content of FA-HPFRC were optimized through wet packing compactness, flowability, mechanical properties and shrinkage tests. Furthermore, the cracking resistance and microstructure of the developed FA-HPFRC were tested and analyzed from macro-micro perspectives. The results show that the volume fractions of AS, cement, FA and SF are determined as 0.482:0.316: 0.109:0.093 when the powder materials in FA-HPFRC are stacked to the most compact state. The wet packing compactness decreases with a higher W/C ratio while it increases first and then decreases with the increase of SP content. Considering the influences on mechanical properties, the W/C and SP content shall be 19% and 1% of the cementitious material separately. The introduction of steel fibers in FA-HPC reduces the concrete's flowability, destroys its dense packing system and lowers its wet packing compactness. However, the characteristics such as high toughness, and large elastic modulus of steel fibers endow FA-HPFRC with excellent mechanical properties, chloride resistance and shrinkage resistance. Especially steel fibers with 12 mm length perform well in improving the comprehensive performance of FA-HPFRC and increasing the cracking resistance 15.03% higher than that of 6 mm steel fibers. This research further improves FA-HPC's mechanical properties and durability, especially the shrinkage cracking resistance, and provides technical and theoretical support for the application of FA-HPFRC.

Tailoring microstructures of carbon fiber reinforced carbon aerogel-like matrix composites by carbonization to modulate their mechanical properties and thermal conductivities

The microstructure evolution of carbon fiber reinforced carbon aerogel-like matrix (C/CA) composites with carbonization temperature and its influence on their properties were investigated. The removal of residual organo-functional groups of the C/CA precursors is dominant when carbonized at 600–750 °C with a large volume shrinkage difference by 17–22% as compared to that at 1200 °C, while the rearrangement of novolac structures is dominant at 900–1200 °C with a slight volume shrinkage fluctuation of 6%. Resultantly, the amount of micropore first increases and then decreases, while the particle size experiences an opposite change. The microstructure correspondingly transforms from a completely amorphous state to a partially amorphous state with graphite crystallites in low-angle misorientation, and then with graphite-like entangling ribbons. Due to the reduced residual tensile stress and increased interfacial bonding, the resulting composites with a variable bulk density of 0.58–0.64 g cm−3 have much higher compressive strengths of 45.8–96.9 MPa than other reported carbon foams or aerogels with similar bulk densities. The increase of strength and modulus with carbonization temperature is mainly due to the smaller tensile stress, higher particle packing compactness, larger microcrystallite size and less residual organo-functional groups. The composites also present a relatively low thermal conductivity of 0.12–0.59 W m−1 K−1. The increase of thermal conductivity with temperature is related to the synergistic effect of reduced phonon scattering associated with smaller specific surface area, larger microcrystallite size and less organo-functional groups and improved phonon transfer associated with increased inter-particle contact area.

Enhancing Persistent Luminescence of Cellulose by Dehydration for Label-Free Time-Resolved Imaging

Organic persistent luminescence is usually emitted from synthesized materials containing π units (aromatic rings, double bonds, etc.). It is challenging but desirable to develop organic materials from renewable resources with tunable persistent luminescence to reduce environmental impact. Herein, we proposed an effective method to enhance the luminescence of cellulose, the most abundant natural renewable material free of π units. It was found that removing the crystal water in cellulose would increase the compactness of molecular packing and stabilize the hydroxyl clusters of polysaccharide chains, consequently leading to significant enhancement of phosphorescence with lifetime up to subseconds. This dehydration induced luminescence enhancement was found in not only purified cellulose but also cellulose-contained substances such as papers, cottons, and many other plant tissues. This indicated easier access to cellulose-based luminescence materials without chemical purification. In addition, label-free time-resolved luminescence imaging of plant tissues was achieved on a smartphone-based apparatus, since endogenous cellulose is distributed extensively in plants. Compared with synthetical luminophores, cellulose is a renewable and biodegradable source abundant in nature, not only readily available but also environmentally friendly. We believe this method may be used to develop other sustainable organic luminescence materials with a lack of π units for various optical applications.

Study on assembling compactness of amphiphilic calixarenes by fluorescence anisotropy

ABSTRACT Understanding the factors that have influence on the compactness of calixarene assemblies is important for choosing or designing molecules for specific function. In this paper, we comparatively investigated the packing performances of a series of amphiphilic calixarene assemblies by fluorescence anisotropy. Calixarene frameworks, the upper-rim decoration of head groups and the length of lower-rim alkyl chains of amphiphilic calixarenes all affect their packing compactness. This work has guiding significance for further application studies.

Experimental Investigation on Improvement of Wet Cooling Tower Efficiency with Diverse Packing Compaction Using ANN-PSO Algorithm

In this study, a numerical and empirical scheme for increasing cooling tower performance is developed by combining the particle swarm optimization (PSO) algorithm with a neural network and considering the packing’s compaction as an effective factor for higher accuracies. An experimental setup is used to analyze the effects of packing compaction on the performance. The neural network is optimized by the PSO algorithm in order to predict the precise temperature difference, efficiency, and outlet temperature, which are functions of air flow rate, water flow rate, inlet water temperature, inlet air temperature, inlet air relative humidity, and packing compaction. The effects of water flow rate, air flow rate, inlet water temperature, and packing compaction on the performance are examined. A new empirical model for the cooling tower performance and efficiency is also developed. Finally, the optimized performance conditions of the cooling tower are obtained by the presented correlations. The results reveal that cooling tower efficiency is increased by increasing the air flow rate, water flow rate, and packing compaction.

Role of Chain Extension in the Ability of Peptide Oligomers to Damage the Lipid Membrane Studied by the l- to d-Amino Acid Substitutions of hIAPP18-27.

Exploration of the relation between the structural feature of oligomers and the ability of oligomers to damage the membrane has been an important subject in the study of the cytotoxic mechanism of amyloid proteins. In this work, we selected the hIAPP18-27 fragment as a model peptide and modified it by an alternating substitution of a d-amino acid for an l-amino acid in the hydrophilic N-terminal region, the hydrophobic C-terminal region, and the entire sequence. We prepared the oligomers using these peptides and investigated the effects of chain extension in different regions of the peptide on the ability of the oligomers to damage the membrane composed of POPC/POPG 4:1. We examined the morphology, structure, surface hydrophobicity, and packing compactness of the oligomers and monitored the changes in the structure and aggregation of the peptides upon interaction with the membrane. We found that the surface hydrophobicity and the disruptive ability of the oligomers are increased by an alternating l- and d-amino acid arrangement in the hydrophobic region of the peptide, while the packing compactness of the oligomers is increased and the disruptive ability of the oligomers decreased by an alternating l- and d-amino acid arrangement only in the hydrophilic region. The extension of the hydrophobic chain plays a significant role in the disruptive ability of the oligomers. Our results suggest that a positive relation between the surface hydrophobicity and the disruptive ability could be established only for the oligomers in which the peptide chains are flexible and loosely packed.

Morphology Reshaping Enabling Self‐Densification of Manganese Oxide Hybrid Materials for High‐Density Lithium Storage Anodes

AbstractMorphology reshaping or reconfiguration, a concept widely used in plastic surgery, energy harvesting, and reconfigurable robots, is introduced for the first time to construct densified electrodes and realize compact Li‐ion storage desirable for high specific energy storage field. Hausmannite‐based hybrid materials, as a proof‐of‐concept prototype, engineered by 1‐methyl‐2‐pyrrolidinone‐soluble surface/interface organic encapsulation, which is crucial in reshaping, exhibit a remarkable increase in the volumetric capacity of more than five times after this process (≈1889 Ah L−1 vs ≈322 Ah L−1). With the simultaneous maintenance of the intrinsic nature, good contact, and no collapsed/agglomerated unit structures of the materials in electrodes, the design affords a maximal increase in the packing compactness and manifests no sacrifice of the reversible ion storage capability (1150 mAh g−1 at 40 mA g−1), stable cycling (≈100% capacity retention), high rate performance (185 mAh g−1 at 10 A g−1), and long lifespan (1000 cycles with 108% capacity retention, ≈455 mAh g−1 at 3 A g−1) for relatively highly loaded electrodes (active materials: 1.20–5.34 mg cm−2). The concept may not only shed new light on fabricating advanced Si‐based and other high capacity–related densified Li storage electrodes but also inject fresh vitality into the field of high‐density power sources.

Small-angle neutron scattering (SANS) and spin-echo SANS measurements reveal the logarithmic fractal structure of the large-scale chromatin organization in HeLa nuclei

This paper reports on the two-scale fractal structure of chromatin organization in the nucleus of the HeLa cell. Two neutron scattering methods, small-angle neutron scattering (SANS) and spin-echo SANS, are used to unambiguously identify the large-scale structure as being a logarithmic fractal with the correlation function γ(r) ∼ ln(r/ξ). The smaller-scale structural level is shown to be a volume fractal with dimension D F = 2.41. By definition, the volume fractal is self-similar at different scales, while the logarithmic fractal is hierarchically changed upon scaling. As a result, the logarithmic fractal is more compact than the volume fractal but still has a rather high surface area, which provides accessibility at all length scales. Apparently such bi-fractal chromatin organization is the result of an evolutionary process of optimizing the compactness and accessibility of gene packing. As they are in a water solution, the HeLa nuclei tend to agglomerate over time. The large-scale logarithmic fractal structure of chromatin provides the HeLa nucleus with the possibility of penetrating deeply into the adjacent nucleus during the agglomeration process. The interpenetration phenomenon of the HeLa nuclei shows that the chromatin-free space of one nucleus is not negligible but is as large as the volume occupied by chromatin itself. It is speculated that it is the logarithmic fractal architecture of chromatin that provides a comfortable compartment for this most important function of the cell.

First-principles investigation of the effect of crystal structure on sulfur isotope fractionation in sulfide polymorphs

In order to study the effect of crystal structure on S isotope fractionation properties of sulfide polymorphs, the reduced partition function ratios of S-34/S-32 (10(3)ln beta(34-32)) for FeS2, CoAsS, ZnS, CdS and MnS polymorphs are calculated in the present study. Our calculations show that 10(3)ln beta(34-32) decreases in the order of pyrite > marcasite > cobaltite > alloclasite > sphalerite approximate to wurtzite > gamma-MnS > hawleyite approximate to greenockite > alabandite. The S coordination number exerts a strong influence on the equilibrium partitioning of S isotopes in these sulfides, and there exist significant S isotope fractionations between the sulfides with different S coordination numbers (CNS), such as alabandite (CNS = 6) and other sulfides (e.g., FeS2, CoAsS, ZnS and CdS polymorphs) (CNS = 4). There is a broad negative correlation between the average bond lengths of all the bonds formed by S and 10(3)ln beta(34-32) values. The compactness of atom packing plays an important role in determining S isotope fractionation properties of sulfides, and S-34 generally tends to concentrate in the phases with higher atomic packing factor (APF). The linear correlation between APF and 10(3)ln beta(34-32) can predict the change of 10(3)ln beta(34-32) with increasing pressure, but pressure has a negligible effect on S isotope fractionation factors between sulfides.

Parallel implicit contact algorithm for soft particle systems

This paper presents a numerical technique to model soft particle materials in which the particles can undergo large deformations. It combines an implicit finite strain formalism of the Material Point Method and the Contact Dynamics method. In this framework, the large deformations of individual particles as well as their collective interactions are treated consistently. In order to reduce the computational cost, this method is parallelised using the Message Passing Interface (MPI) strategy. Using this approach, we investigate the uniaxial compaction of 2D packings composed of particles governed by a Neo-Hookean material behaviour. We consider compressibility rates ranging from fully compressible to incompressible particles. The packing deformation mechanism is a combination of both particle rearrangements and large deformations, and leads to high packing fractions beyond the jamming state. We show that the packing strength declines when the particle compressibility decreases, and the packing can deform considerably. We also discuss the evolution of the connectivity of the particles and particle deformation distributions in the packing.

Compaction algorithm for orthogonal packing problems

The article is devoted to an algorithm for increasing the density of placement schemes in orthogonal packing problems. The proposed heuristic packing compaction algorithm is based on the principle of local replacement of placed objects located as far from the origin of a container as well as located near the local free spaces inside it. The algorithm uses a list of six rules which select objects from a container for deleting and subsequent reallocation of them into freed spaces of the container. The article contains results of computational experiments carried out on the standard strip packing problems.

Polymer Assemblies with Nanostructure-Correlated Aggregation-Induced Emission

The correlation of aggregation-induced emission (AIE) to the nanostructure of polymer assemblies was investigated. A series of AIE-active PDMA-b-P(BzMA-TPE) [PDMA: poly(N,N-dimethylaminoethyl methacrylate); P(BzMA-TPE): poly[benzyl methacrylate-co-1-ethenyl-4-(1,2,2-triphenylethenyl)benzene]] assemblies with controlled nanostructures were prepared via polymerization-induced self-assembly of BzMA and TPE, an AIEgen, in the presence of PDMA macro-chain-transfer agents. We found that the fluorescence intensity and fluorescent quantum yield increase in the order of vesicles > wormlike micelles > spherical micelles. For spherical micelles and vesicles, the AIE effect strengthens with increase in micellar size and wall thickness, respectively. As the AIE effect indicates the packing compactness of the AIEgens, the discovered structure-correlated emission can be attributed to the stress variation of polymer chains in the aggregates. AIE is therefore potentially useful as a probe for the investigation and underst...

Generation of dense granular deposits for porosity analysis: assessment and application of large-scale non-smooth granular dynamics

The knowledge of structural properties of granular materials such as porosity is highly important in many application-oriented and scientific fields. In this paper we present new results of computer-based packing simulations where we use the non-smooth granular dynamics (NSGD) method to simulate gravitational random dense packing of spherical particles with various particle size distributions and two types of depositional conditions. A bin packing scenario was used to compare simulation results to laboratory porosity measurements and to quantify the sensitivity of the NSGD regarding critical simulation parameters such as time step size. The results of the bin packing simulations agree well with laboratory measurements across all particle size distributions with all absolute errors below 1%. A large-scale packing scenario with periodic side walls was used to simulate the packing of up to 855,600 spherical particles with various particle size distributions (PSD). Simulation outcomes are used to quantify the effect of particle-domain-size ratio on the packing compaction. A simple correction model, based on the coordination number, is employed to compensate for this effect on the porosity and to determine the relationship between PSD and porosity. Promising accuracy and stability results paired with excellent computational performance recommend the application of NSGD for large-scale packing simulations, e.g. to further enhance the generation of representative granular deposits.

Enhanced Molecular Recognition between Nucleobases and Guanine-5'-monophosphate-disodium (GMP) by Surfactant Aggregates in Aqueous Solution.

Only specific base pairs on DNA can bind with each other through hydrogen bonds, which is called the Watson-Crick (W/C) pairing rule. However, without the constraint of DNA chains, the nucleobases in bulk aqueous solution usually do not follow the W/C pairing rule anymore because of the strong competitive effect of water and the multi-interaction edges of nucleobases. The present work applied surfactant aggregates noncovalently functionalized by nucleotide to enhance the recognition between nucleobases without DNA chains in aqueous solution, and it revealed the effects of their self-assembling ability and morphologies on the recognition. The cationic ammonium monomeric, dimeric, and trimeric surfactants DTAB, 12-3-12, and 12-3-12-3-12 were chosen. The surfactants with guanine-5'-monophosphate-disodium (GMP) form micelles, vesicles, and fingerprint-like and plate-like aggregates bearing the hydrogen-bonding sites of GMP, respectively. The binding parameters of these aggregates with adenine (A), uracil (U), guanine (G), and cytosine(C) indicate that the surfactants can promote W/C recognitions in aqueous solution when they form vesicles (GMP/DTAB) or plate-like aggregates (GMP/12-3-12) with proper molecular packing compactness, which not only provide hydrophobic environments but also shield non-W/C recognition edges. However, the GMP/12-3-12 micelles with loose molecular packing, the GMP/12-3-12 fingerprint-like aggregates where the hydrogen bond sites of GMP are occupied by itself, and the GMP/12-3-12-3-12 vesicles with too strong self-assembling ability cannot promote W/C recognition. This work provides insight into how to design self-assemblies with the performance of enhanced molecule recognition.

Inversion twinning in a second polymorph of the hydrochloride salt of the recreational drug ethylone.

A second polymorph of the hydrochloride salt of the recreational drug ethylone, C12H16NO3(+)·Cl(-), is reported [systematic name: (±)-2-ethylammonio-1-(3,4-methylenedioxyphenyl)propane-1-one chloride]. This polymorph, denoted form (A), appears in crystallizations performed above 308 K. The originally reported form (B) [Wood et al. (2015). Acta Cryst. C71, 32-38] crystallizes preferentially at room temperature. The conformations of the cations in the two forms differ by a 180° rotation about the C-C bond linking the side chain to the aromatic ring. Hydrogen bonding links the cations and anions in both forms into similar extended chains in which any one chain contains only a single enantiomer of the chiral cation, but the packing of the ions is different. In form (A), the aromatic rings of adjacent chains interleave, but pack equally well if neighbouring chains contain the same or opposite enantiomorph of the cation. The consequence of this is then near perfect inversion twinning in the structure. In form (B), neighbouring chains are always inverted, leading to a centrosymmetric space group. The question as to why the polymorphs crystallize at slightly different temperatures has been examined by density functional theory (DFT) and lattice energy calculations and a consideration of packing compactness. The free energy (ΔG) of the crystal lattice for polymorph (A) lies some 52 kJ mol(-1) above that of polymorph (B).

Pressure-Dependent Properties of Elementary Hydrophobic Interactions: Ramifications for Activation Properties of Protein Folding.

Hydration effects on a pair of methane molecules are investigated by extensive constant-pressure (NPT) sampling using the TIP4P model of water under 1, 1000, 2000, and 3000 atm. The volume distributions of pure water and of methanes plus water are determined directly as functions of methane-methane distance ξ. The corresponding excess isothermal and adiabatic compressibilities are estimated from the pressure-dependent methane excess volume. The dependence of excess volume on ξ is oscillatory for small ξ. The maxima of excess volume and compressibility are seen near the desolvation barrier (db) of the potential of mean force (PMF). These features may be understood by the development, near the db, of a void volume encased by a molecular (Connolly) surface defined using a water-sized probe. These db properties for two methanes are consistent with well-corroborated experimental observations of positive activation volumes for protein folding and some experiments suggesting a slightly higher compressibility for the folding transition state than the unfolded state. At high pressures, the volumes at the PMF solvent-separated minimum and the contact-minimum configurations are both smaller than the volume at large ξ. This trend provides a rationalization for the compactness of pressure-denatured states of proteins. Taking the packing densities of pure nonpolar phases into consideration, our simulation results suggest that whether the activation volume of unfolding is positive or negative hinges on the packing compactness of the protein core. Volume change can be but is not necessarily monotonic along the folding pathway.