Three-dimensional Solubility Parameters Research Articles

Systematic Investigation on the Swelling Response and Oil Resistance of NBR Using the Prediction Models Determined by the Modified Flory-Huggins Interaction Parameter.

The equilibrium swelling test was employed to determine the swelling response of Nitrile Butadiene Rubber (NBR) with various acrylonitrile (ACN) contents, and the three-dimensional solubility parameter (HSP) and modified Flory-Huggins interaction parameter (χHSP) were used to establish the prediction model of the oil-resistant property. The results indicate that the energy difference (Ra) between NBR and solvents calculated by HSP values can be correlated with the swelling response qualitatively with an inversed "S-shape", and high swelling response occurs at Ra < 8 MPa1/2 for NBR. For the purpose of establishing the prediction model, the new modified χHSP value has been calculated and fitted with the swelling response using exponential and logarithmic fittings, respectively. Two prediction models considering all the possible influencing factors have been obtained to determine the swelling response and oil resistance of NBR-based rubber products in bio-fuels, represented by the bio-diesel and IRM 903 test oil in this work. The swelling response of NBR can be evaluated precisely, and high swelling regions can be predicted and avoided in the new emerging fuels through the prediction models. Thus, the oil resistance of NBR-based rubber products, such as seals, holes and gaskets can be well predicted now.

Determination of carbon nanoparticle dispersion solubility parameters using the classic Hansen and the DiPEVa method

Hansen's three-dimensional Solubility Parameter (3DSP) are widely recognized for assessing the compatibility of a dispersed phase with a continuous phase. A modified approach, known as the DiPEVa method, has recently emerged in the literature. This method refines 3DSP by incorporating surface tension considerations. Given the presence of these two similar methodologies, the objective of this study is to conduct a comparative analysis between the two approaches, employing carbon nanoparticles, including graphene oxide, carbon quantum dots (produced via microwave pyrolysis of Spirulina microalgae, and the reaction between citric acid and ethylenediamine), graphene nanoplatelets, and carbon nanotubes as the focal subjects. To achieve this, assessing solubility parameters involved dispersing these nanoparticles in 32 organic solvents with well-established solubility parameters. Subsequently, the collected data underwent a genetic algorithm optimization, facilitating the computation of the Hansen 3D dispersibility sphere. This process included the calculation of the 3DSP for the sphere's central point and its interaction radius (R0). Quality-of-fit metrics, such as DataFit values and the percentage of outliers, were computed to assess the accuracy of the models. As a result, it was evident that the DiPEVa method outperformed the Hansen method in most cases, except for carbon quantum dot dispersion obtained through Spirulina pyrolysis, where both methods yielded comparable results.

Study on the application of Flory–Huggins interaction parameters in swelling behavior and crosslink density of HNBR/EPDM blend

The sorption and permeation coefficients of four amine solvents in hydrogenated nitrile rubber/ethylene propylene diene monomer rubber (HNBR/EPDM) blends were calculated, and the transport mechanism of solvents was verified by the Peppas–Sahlin model. The Flory–Huggins interaction parameters (χ: χ1D and χ3D) between solvent and HNBR/EPDM blend were obtained by one-dimensional solubility parameter (SP-1D) and three-dimensional solubility parameter (SP-3D), respectively. The predictive powers of χ1D and χ3D on the transport behavior of amine solvents permeating in HNBR/EPDM blends were studied and compared. The application of χ1D and χ3D in the calculation of cross-linking density was explored. It is found that the χ3D is more suitable for predicting the transport behavior of solvents with both strong and weak polarity in the blends, while the χ1D is only available for the solvents with poor polarity. However, the χ1D is more appropriate to calculate the crosslink densities of HNBR/EPDM blends.

DiPEVa, an interactive method for adjusting the three-dimensional solubility parameters to surface tension

There has been increased interest recently in studies that use the surface tension parameter to predict the dispersion behavior of liquids at the level of nanotechnology. These same studies use the solubility parameter methodology to assess the compatibility of these liquid mixtures. Both parameters have been analyzed separately, despite being closely linked by well-known physicochemical relationships. The present study deepens the interrelationship between these two parameters, proposing innovative three-dimensional solubility parameters (3DSP) adjusted for surface tension. Through this, it is possible to obtain the 3DSP components that can be used to model applications that depend heavily on surface tension, such as emulsions, inorganic dispersion, solvent and cosolvent selection, encapsulation processes, among others.

A new method to measure the three-dimensional solubility parameters of acrylate rubber and predict its oil resistance

As people pay more and more attention to environmental protection and the high cost of diesel and gasoline, in order to reduce environmental pollution and use cost, some low-pollution and low-cost components, such as alcohols (ethanol, etc.) and esters (methyl acetate, etc.), are added to diesel and gasoline. Due to the addition of new components, the swelling degree of rubber products will also change. In the literature, this method is often used to test the oil resistance of vulcanizates directly by immersing them in oil. In this paper, a new method is used to predict the oil resistance of vulcanizates. In order to investigate the swelling property of acrylate rubber more comprehensively and predict its oil resistance, the swelling behavior of carboxylic acrylate rubber (AR12) produced by Zeon Corporation (Japan) was measured by swelling method in 24 different organic solvents, and the value of one-dimensional solubility parameter (δ) of AR12 was obtained, ranging from 18 to 22 MPa1/2. The swelling data were analyzed by Hansen Solubility Parameter in Practice software, and the three-dimensional solubility parameter sphere, two-dimensional solubility parameter graph and three-dimensional solubility parameter of AR12 were thus obtained. The values of the three-dimensional solubility parameter of AR12 were δd = 18.30 MPa1/2, δp = 7.10 MPa1/2 and δh = 5.60 MPa1/2, respectively. There is an energy difference (Ra) between AR12 and the 24 solvents, and the swelling ratio (q) of AR12 in the 24 solvents presents an inverse “S”-shaped curve as the Ra values between them change. The experimental results proved that the three-dimensional solubility parameters were more accurate in predicting swelling performance than that of one-dimensional solubility parameter. To verify the experimental results, the relationships of Ra, q and δt values with the volume fractions of two groups of solvent mixtures were established. The experimental results showed the same as those obtained by a single solvent, which further proved the correlation of rubber swelling responses. This new method can be used to predict the oil resistance of rubber, and its advantages compared to traditional methods are using more environmentally friendly and cheaper liquid instead of toxic or expensive liquid. This method can be used not only to evaluate acrylate rubber, but also predict the oil resistance of other polymers.

Optimization determination of three-dimensional solubility parameters of fluororubber F2603

Turbidity titration experiment on fluororubber F2603 using a variety of good solvents and poor solvents, the minimum volume closure ellipsoidal fit is performed on the 48 cloud point data generated by KY (Kumar and Yildirim) first-order algorithm, thus determining the ellipsoid The ball center is a three-dimensional solubility parameter: δd=16.63(MPa)1/2; δp=11.25(MPa)1/2; δH=12.02(MPa)1/2, and the solubility parameter is 23.40(MPa)1/2.The reliability and accuracy of the fitting results are determined by the group contribution method, The solubility parameters have important guiding significance for selecting solvents with superior performance and determining better formulation design.

Effect of crosslink density on solubility parameters of styrene butadiene rubber and the application in pre-screening of new potential additives

Equilibrium swelling measurement and software program were employed to investigate the effect of crosslink density on the swelling responses and three-dimensional solubility parameters (HSP) of the cured SBR samples. The swelling responses change evidently with increased crosslink densities which, however, have no influence on the HSP values of SBR. In order to study the application of HSP in predicting interactions between rubbers and additives, a set of new Flory-Huggins interaction parameters (χHSP) was calculated by HSP values, and was further correlated with the correlation index, which was obtained by normalizing the swelling data. The results showed that the swelling ratio decreased linearly with increasing χHSP value. The slope of these linear relations obtained for each SBR group decreased with increasing crosslink density in the form of power function. On the contrary, the relationship obtained between the correlation index and χHSP value had no change with the crosslink density. Taking advantage of this study, one can easily make the pre-screening of potential additives for their suitability in the rubber formula design.

Estimation of Three-Dimensional Solubility Parameters of DM-700 Polyester Resin by Turbidity Titration

According to the method of turbidity titration and 63 cloud point data minimum volume closure ellipsoid fitting, the solubility parameter of polyester resin DM-700 was determined to be 22.84(MPa)1/2, and the three-dimensional solubility parameter was (δd=17.15 (MPa)1/2; δp=9.97(MPa)1/2; δH=11.32(MPa)1/2). This value is close to the result calculated by the group contribution method (22.68(MPa)1/2), which further proves that the method is accurate and reliable.

Determination of three-dimensional solubility parameters of styrene butadiene rubber and the potential application in tire tread formula design

Equilibrium swelling measurement was employed to correlate the Hildebrand (one-dimensional) solubility parameter (δ) of styrene butadiene rubber (SBR) with using different kinds of solvents. The δ was estimated to be a range from 17 MPa1/2 to 19 MPa1/2. It was attempted to calculate the three-dimensional solubility parameter (HSP) of SBR by inputting the swelling data into a professional software program, and the output results were δd = 18.0 MPa1/2, δp = 2.9 MPa1/2 and δH = 2.3 MPa1/2. A new Flory-Huggins interaction parameter (χHSP) between SBR and solvents was calculated by HSP values for the purpose of better predicting rubber swelling responses. The results turned out that the swelling ratio (q) increased with a decrease of χHSP value, showing a roughly linear relationship. Furthermore, a correlation index relating to χHSP value was introduced and mathematical fitted as a functional equation in this work. By using this equation, it is easy to characterize the relative interactions between SBR and each ingredient involved in the formulation and make a pre-screening of the candidate additives for the formula design. Taking advantage of this method one can response better to the challenges in selecting the most suitable additives and replacing the outdated ones by the new emerging ones, bio-sourcing with environmentally friendly ones in particular.

Prediction of Molecular Affinity on Solid Surfaces via Three-Dimensional Solubility Parameters Using Interfacial Free Energy as Interaction Threshold

Various adhesive and wetting phenomena in nature and practical applications originate from the interaction between the surfaces of materials and other substances. In this study, we developed a method for calculating the Hansen solubility parameters (HSP) of the surface of the solid materials to elucidate the surface interaction by quantitatively and visually representing adsorptivity with a three-dimensional vector. The HSP were derived from the interfacial free energy, which can easily be calculated from the contact angles of three organic solvents on the solid materials. The HSP for a glassy carbon (GC) surface calculated using our method were correlated with the adsorptivity on the GC surface of several organic molecules. The adsorptivity was evaluated using electrochemical impedance spectroscopy and molecular mechanics simulations; the latter of which also revealed that the HSP calculated for the Pt surface were highly correlated with its interactivity. Moreover, the HSP of the polytetrafluoroethylene (PTFE) surface obtained herein appropriately reflect the molecular structure of PTFE. The results underpin that our method enables the elucidation of various surface phenomena involving noncovalent interaction and allows the affinity between solid surfaces and tens of thousands of substances recorded in the HSP database to be predicted.

Predictive power in oil resistance of fluororubber and fluorosilicone rubbers based on three-dimensional solubility parameter theory

Equilibrium swelling test was employed to determine the swelling responses of Fluororubber (FKM) and Fluorosilicone Rubber (FVMQ) in different types of solvents, and the one-dimensional solubility parameters of FKM and FVMQ were obtained with a range of 17–25 MPa1/2 and 16–20 MPa1/2 respectively. It was attempted to calculate the three-dimensional solubility parameters (HSP) of FKM and FVMQ by using a professional computer software, and a new type of bio-fuel, represented by biodiesel, was further selected as an object in this work to investigate its swellability. Flory-Huggins interaction parameter (χHSP) between FKM, FVMQ and each solvents used in this work was calculated by HSP values, and the results turned out that the swelling ratio (q) decreased with increasing χHSP value. By mathematical fitting, two functional relationships between q and χHSP for FKM and FVMQ were achieved to predict the swelling properties of rubber in fluids. The increasing use of biodiesel with their effect on rubber materials has become an important topic of industrial research. The second components, including ethanol and ethylene glycol, were added into biodiesel with the purpose of cost reduction, which however might cause a critical increase of rubber swelling. One of the possible applications of χHSP values is the prediction or explanation of swelling behavior. Therein, χHSP values between FKM, FVMQ and biodiesel/additive blends were calculated and found that χHSP firstly decreased and then increased with increase of the additive (ethanol and ethylene glycol) content. Taking advantage of this tendency one can predict the swelling properties of rubber products in the biodiesel blends and provide an important reference for such applications in liquid medium.

PROCEDURE FOR ESTIMATING OIL THREE-DIMENSIONAL SOLUBILITY PARAMETERS

ABSTRACT Process oils make important contributions to nearly every compound in a tire, and oil–polymer interactions have effects on compound processing and performance. One way to predict oil–polymer interactions is to determine the three-dimensional (3-D) Hansen solubility parameters (HSPs) for both oil and polymer, and the polymer solubility sphere (PSS) radius. Favorable oil–polymer interactions occur when an oil's HSPs are located within a PSS. Interactions are stronger when an oil's HSPs are located closer to the center of the PSS. If an oil's HSPs are located outside a polymer's solubility sphere, then the polymer is not soluble in the oil as a result of insufficient favorable interactions. A polymer characterization technique for determining the HSPs is the bitumen solubility model. However, no simple procedure has previously been documented for estimating the 3-D HSPs for an oil. A labor-intensive method has been described by Levin and Redelius. The oil solubility parameters estimation procedure (OSPEP) has been developed to meet the need for a relatively simple characterization technique. This procedure can provide an estimation of oil HSPs by running two titrations and a dynamic scanning calorimetry test. Analysis involves an iterative procedure to estimate the three HSPs for the oil. OSPEP represents a step forward to easily obtain insight into oil–polymer interactions.

Investigation of the Swelling and Network Parameters of Epoxy Coatings Containing Polyaniline

The kinetics of swelling of epoxy coatings modified with polyaniline is investigated. The influence of the three-dimensional solubility parameter, the dielectric permeability, and the molar volume of solvent on the swelling of epoxy polymer coatings is shown. The parameters of the three-dimensional network for epoxy coatings modified with polyaniline are calculated.

Solubility parameters of hypromellose acetate succinate and plasticization in dry coating procedures

Solubility parameters of HPMCAS have not yet been investigated intensively. On this account, total and three-dimensional solubility parameters of HPMCAS were determined by using different experimental as well as computational methods. In addition, solubility properties of HPMCAS in a huge number of solvents were tested and a Teas plot for HPMCAS was created. The total solubility parameter of about 24 MPa0.5 was confirmed by various procedures and compared with values of plasticizers. Twenty common pharmaceutical plasticizers were evaluated in terms of their suitability for supporting film formation of HPMCAS under dry coating conditions. Therefore, glass transition temperatures of mixtures of polymer and plasticizers were inspected and film formation of potential ones was further investigated in dry coating of pellets. Contact angles of plasticizers on HPMCAS were determined in order to give a hint of achievable coating efficiencies in dry coating, but none was found to spread on HPMCAS. A few common substances, e.g. dimethyl phthalate, glycerol monocaprylate, and polyethylene glycol 400, enabled plasticization of HPMCAS; however, only triethyl citrate and triacetin were found to be suitable for use in dry coating. Addition of acetylated monoglycerides to triacetin increased coating efficiency, which was likewise previously demonstrated for triethyl citrate.

Hansen solubility parameters of polyglycolic acid and interaction parameters between polyglycolic acid and solvents

This article focuses on the solubility parameters and interaction parameters of polyglycolic acid. 43 solvents have been used for polyglycolic acid to study the dissolution property. Then the Hansen three-dimensional solubility parameters and total parameter of polyglycolic acid were obtained by an optimization calculation. The values of δd, δp, δh and δ for polyglycolic acid have been obtained as 17.094(J/cm3)1/2, 8.206(J/cm3)1/2, 7.912(J/cm3)1/2 and 20.546(J/cm3)1/2. It was proved that the total parameter of polyglycolic acid is creditable by intrinsic viscosity approach and group contribution method. The values of the interaction parameter and the solubility parameter “distance” between polyglycolic acid and 43 solvents have been calculated. The results of the interaction parameters accords well with the standard of complete miscibility suggested by Flory–Huggins for polymers and solvents.

Investigation on Three-Dimensional Solubility Parameters for Explanation and Prediction of Swelling Degree of Polydimethylsiloxane Pervaporation Membranes

Using polydimethylsiloxane (PDMS) as a basic matrix to prepare ethanol and butanol permselective pervaporation membranes is a vibrant field. Many studies have verified that the three-dimensional Hansen solubility parameters (HSP) theory offers a valid explanation for the swelling performance of ethanol and butanol in PDMS. Five parameters (δD, δP, δH, δt, and Ra) are defined in HSP theory which can be individually used to explain the interaction strength between a solvent and a polymer. However, for the above five parameters, which one is the most effective parameter for deciding the swelling degree still needs to be determined. In this study, a commonly used hydroxy-terminated PDMS precursor was adopted to prepare the PDMS network. The HSP of the chosen PDMS precursor was measured by an advanced “solubility-rating” method. The special software package HSPiP (4.1.03), purchased from the HSPiP team, was used to process the “solubility-rating” results. The equilibrium swelling degree (Q value) of the PDMS network in water, ethanol, butanol, and toluene was measured and the relationships between the five HSP parameters of the solvents and the logarithmic equilibrium swelling degree, log(Q), were discussed. It was found that the measured polar parameter, δP, of PDMS was 0.12 MPa0.5. The measured hydrogen bonding parameter, δH, was larger than δP, attaining a value of 8.6 MPa0.5, because the hydroxy groups directly contributed to the hydrogen bonding solubility parameter, δH. With respect to the relationships between log(Q) and δD, δP, δH, δt, and Ra, linear relationships existed after plotting log(Q) vs. δP and log(Q) vs. δH. The linear relation degree of the fitted lines was 0.995 and 0.989, respectively. Their standard deviations were 0.149 and 0.232, respectively. Therefore, a better linear relationship existed between log(Q) and δP than the other solubility parameters. This indicated that the polar interaction was the main effect for deciding the swelling degree of the PDMS network in water and alcohol systems.

Quantitative exploration of the swelling response for carbon black filled hydrogenated nitrile rubber with three-dimensional solubility parameters

Equilibrium swelling data with a range of solvents for non-filled cured rubber samples were used to determine Hansen three-dimensional solubility parameters (HSPs) of seven HNBR grades with nominal acrylonitrile contents from 21 to 49 % using the HSPiP computer program. The results showed that the increase of acrylonitrile contents for HNBR grades led to increase of polar component (δ p) and hydrogen bonding component (δ h), but with little changes of dispersion component (δ d). By using the so far obtained HSPs it is possible to explain and predict the swelling behaviors of the fully formulated HNBR-based vulcanizates in industrial oils (IRM 903 was selected for testing), in a reference bio-fuel (Fuel C was selected for testing) and in bio-diesel (FAME was selected for testing). In these liquids, the volume swellings decreased with increasing of Ra values (calculated by HSPs), and to a certain extent, can be calculated with a modified Flory–Rehner equation by assuming that fillers would not swell in question.

Investigation of the swelling response and quantitative prediction for hydrogenated nitrile rubber

A much more elegant method using three groups of solvent mixtures was employed to determine the Hansen three-dimensional solubility parameters (HSPs) of hydrogenated nitrile rubber (HNBR). The HSPs obtained by this way are comparable with previous work. The Flory-Rehner relationship was used to investigate the effects of the crosslink density and the molar volume of solvent on the swelling response of the HNBR matrix. Both of these factors have a significant effect on the swelling volume in high swelling conditions (small Ra and Mc values) while the swelling curves show the characteristic reversed S-shape. The swelling volumes of HNBR (Therban 2568) in solvents and solvent mixtures have been calculated quantitatively by the Flory-Rehner relationship and correlated with the energy difference (Ra). The calculated swelling volumes decrease with increasing Ra values and also show the characteristic reversed S-shape, which correlate well with the experimental values. Therefore, it is expected that the swelling behavior of HNBR based vulcanizates in mixed fluids, taking bio-fuels and bio-based service fluids as examples, may now be predicted quantitatively.

A new way to determine the three-dimensional solubility parameters of hydrogenated nitrile rubber and the predictive power

In order to understand the swelling behavior of hydrogenated nitrile rubber (HNBR) more fully, the total solubility parameters (δt) of HNBR (Therban 2568) were determined by equilibrium swelling tests. Then, the swelling responses were analysed by a computer program to determine the Hansen three-dimensional solubility parameter (HSP). The HSP values – determined from lightly cured rubber samples – were estimated as δd = 18.4 (J/cm3)1/2, δp = 6.0 (J/cm3)1/2, δh = 4.5 (J/cm3)1/2 and δt = 19.9 (J/cm3)1/2. The energy difference (Ra) between HNBR and solvents or solvent mixtures have been calculated by their HSP values and proven to be useful for predicting the swelling behaviour of HNBR. The swelling volume decreases with increasing Ra values. Using blended solvents, a clear correlation between Ra values and the rubber swelling response was established. Thus, it may be possible to use the Hansen three-dimensional solubility parameters to predict swelling phenomena of cured rubber articles in mixed fluids such as bio-fuels or lubricants. Also, the HSP values may be used to predict the response of rubber seals or gaskets when replacing toxic or expensive fluids with more favorable environmentally friendly or inexpensive ones.

Prediction of Drug–Polymer Miscibility through the use of Solubility Parameter based Flory–Huggins Interaction Parameter and the Experimental Validation: PEG as Model Polymer

Important consideration for developing physically stable solid dispersion is miscibility of drug in carrier matrix. It is possible to predict thermodynamics of binary system through free energy calculations based on Flory-Huggins interaction parameter (χ(dp)). In present study, PEG 6000 as model polymer and dataset comprising commonly used drugs/excipients was selected. The three-dimensional solubility parameter based on group contribution method was utilized for systemic calculation of χ(dp) of the polymer with each compound in data set. On the basis of the values of χ(dp), it was possible to categorize all the compounds into three distinct categories, Types I and II: compounds predicted to be miscible and immiscible respectively with the polymer in all proportions and Type III: compounds expected to exhibit composition dependent miscibility behavior. The Bagley plot showed that majority of points for Type I fall in a region, which can approximately be delimited by a circle. Experimental verification through thermal analysis revealed that though it was possible to predict correctly miscibility behavior of Type II class compounds, distinction between Types I and III was less evident. Hence, solubility parameter based χ(dp) may be used as an initial tool for fast screening of immiscible combination of polymer and drug.