Physical and textural characteristics of some North American shortenings

A number of North American vegetable and animal fat shortenings were evaluated for their melting, crystallization, textural and polymorphic crystal characteristics and solid fat content (SFC). The majority of the dropping points and crystallization temperatures of the fats ranged from 42 to 46°C and from 27 to 31°C, respectively. Softening points of the products were higher than the dropping points of their fats, especially for the vegetable shortenings. Differential scanning calorimetry melting curves of the products were different for the various products. The animal fat shortenings were mainly in theβ-polymorphic form, while vegetable shortenings containing palm oil were in theβ′ form. Textural evaluation was carried out on the products with the cone penetrometer, constant speed penetration and constant speed compression. Constant speed compression supplied a measure of brittleness and a degree of viscosity. Lard and shortenings containing high levels of palm oil were able to withstand large deformations without breakage. The effect of tempering temperature of the fat in the SFC determination was evaluated and the values obtained were compared with the SFC of the actual product. SFC of fat and product were determined by pulse nuclear magnetic resonance. Correlation of values within textural methods was significant (P<..01), but were not significant between texture and SFC of the fat, indicating that the nature of the crystal network also plays a role in texture.     

Modelling lipase‐catalysed transesterification of fats containing n‐3 fatty acids monitored by their solid fat content

Transesterification of fat blends rich in n‐3 polyunsaturated fatty acids (n‐3 PUFA), catalysed by a commercial immobilised thermostable lipase from Thermomyces lanuginosa, was carried out batch‐wise. Experiments were performed, following central composite rotatable designs (CCRDs) as a function of reaction time, temperature and media formulation. Mixtures of palm stearin, palm kernel oil and a commercial concentrate of triacylglycerols rich in n‐3 PUFA (“EPAX 2050TG” in CCRD‐1 and “EPAX 4510TG” in CCRD‐2) were used. The time‐course of transesterification was indirectly followed by the solid fat content (SFC) values of the blend at 10 °C, 20 °C, 30 °C and 35 °C. A decrease in all SFC values of the blends at 10 °C, 20 °C, 30 °C and 35°C was observed upon transesterification. The SFC_{10 °C} and SFC_{20 °C} of transesterified blends varied between 18 and 48 and SFC_{35 °C} between 6 and 24. These values fulfil the technological requirements for the production of margarines. Under our conditions, lipid oxidation may be neglected. However, the accumulation up to 8.3% free fatty acids in reaction media is a problem to overcome. The development of response surface models, describing both the final SFC value and the SFC decrease, will allow predicting results for novel proportions of fats and oils and/or a novel combination time‐temperature.     

复合可聚合乳化剂制备高固含量低黏度聚丙烯酸酯乳液

以DNS-86和F-6为复合可聚合乳化剂APS为引发剂,MMA、BA为单体采用半连续法制备20%固含量种子乳液,以种子乳液为介质,选用4种不同类型乳化剂:非离子可聚合乳化剂F-6,阴离子可聚合乳化剂DNS-86、常规非离子乳化剂OP-10、常规阴离子乳化剂SDS进行不同组合,同时滴加预乳化液、引发剂、缓冲剂直接二次成核制备62%固含量二元粒径分布乳液。重点研究了乳化剂复合方式、用量及配比、反应温度等对聚合稳定性、乳液流变性等的影响。,     

Plastic fats with zero trans fatty acids by interesterification of mango,mahua and palm oils

Speciality plastic fats with no trans fatty acids suitable for use in bakery and as vanaspati are prepared by interesterification of blends of palm hard fraction (PSt) with mahua and mango fats at various proportions. It was found that the interesterified samples did not show significant differences in solid fat content (SFC) after 0.5 or 1 h reaction time. The blends containing PSt/mahua (1:1) showed three distinct endotherms, indicating a heterogeneity of triacylglycerols (TG), the proportions of which altered after interesterification. The SFC also showed improved plasticity after interesterification. Similar results were observed with other blends of PSt/mahua (1:2). These changes in melting behavior are due to alterations in TG composition, as the trisaturated‐type TG were reduced and the low‐melting TG increased after interesterification. The blends containing PSt/mango (1:1) showed improvement in plasticity after interesterification, whereas those containing PSt/mango (2:1) were hard and showed high solid contents at higher temperature and hence may not be suitable for bakery or as vanaspati. The blends with palm and mahua oils were softer and may be suitable for margarine‐type products. The results showed that the blends of PSt/mahua (1:1, 1:2) and PSt/mango (1:1) after interesterification for 1 h at 80 °C showed an SFC similar to those of commercial hydrogenated bakery shortenings and vanaspati. Hence, they could be used in these applications in place of hydrogenated fats as they are free from trans acids, which are reported to be risk factors involved in coronary heart disease. For softer consistency like margarine applications, the blends containing palm oil and mahua oil are suitable.     

Pattern recognition of lipase‐catalyzed or chemically interesterified fat blends containing n‐3 polyunsaturated fatty acids

The feasibility to discriminate among samples of different fat blends prior and after inorganic or lipase‐catalyzed interesterification, via pattern recognition techniques [principal component analysis (PCA) and discriminant analysis (DA)], was investigated. Blends I and II, consisting of mixtures of palm stearin, palm kernel oil and a concentrate of triacylglycerols (TAG) rich in n‐3 polyunsaturated fatty acids (EPAX 4510TG or EPAX 2050TG) were used. These blends, prior (64 samples) and after interesterification, catalyzed by an immobilized Thermomyces lanuginosa lipase (Lipozyme TL IM, 54 samples) or by sodium methoxide (10 samples), were characterized by their acylglycerol profiles (25 chromatographic peaks) and solid fat content (SFC) at 10, 20, 30 and 35 °C. PCA on the multivariate data (i) showed that the initial samples were characterized by higher SFC and higher contents of high‐melting TAG and (ii) suggested two separate clusters of initial and interesterified samples. DA was performed on the multivariate data to determine which of the 29 variables have discriminative power. When the 124 samples, characterized by their acylglycerols, were grouped into (i) initial and interesterified samples of blends I or II (four groups) or (ii) also by the catalyst used (six groups), 98.4% of the samples were correctly classified.     

Nucleation behavior of blended high‐melting fractions of milk fat as affected by emulsifiers

The effect of highly hydrophobic emulsifiers, the palmitic sucrose ester P‐170 (hydrophilic/lipophilic balance (HLB) = 1.0), the stearic sucrose ester S‐170 (HLB = 1.0), the polyglycerol ester decaglycerol decastearate DAS 7S (HLB = 3.7) and the polyglycerol ester decaglycerol dodecabehenate DDB 750 (HLB = 2.6), on the nucleation of a high melting point milk fat fraction (HMF) and its blends with sunflower oil (SFO) was investigated by polarized laser light turbidimetry, X‐ray diffractometry and polarized light microscopy (PLM). Addition of polyglycerol esters accelerated nucleation, giving shorter induction times for the same supercooling. On the contrary, sucrose esters inhibited nucleation since induction times were elongated in all conditions selected. Addition of emulsifiers modified the polymorphic behavior in the blends with SFO. The β' form was promoted especially with the addition of S‐170. DAS 7S and DDB 750 promoted crystallization. PLM images showed many small crystals that did not appear in HMF images. Addition of P‐170 and S‐170 delayed nucleation and inhibited crystal growth. Crystals were notoriously smaller than the ones that appeared in HMF images. The Fisher–Turnbull model was used to calculate activation free energies of nucleation. In all cases, sucrose esters elevated the energy barrier for nucleation. Polyglycerol esters, however, if they had an effect on the energy barrier, lowered the values.     

Polymorphic stability of some shortenings as influenced by the fatty acid and glyceride composition of the solid phase

A number of North American vegetable and animal fat shortenings, which had been analyzed previously for their physical and textural characteristics, were analyzed also for their chemical composition. The fatty acid and triglyceride composition of the solids were calculated by analyzing the composition of the original product and the liquid phase, and by determination of the solid fat content (SFC) of the fat. The solids were also isolated by isopropanol (IP) separation, and the high melting glycerides (HMG) by acetone crystallization at 15°C. There was not much difference in total saturates andtrans content between vegetable and animal fat shortenings. Changing formulations from soy-palm to soy-cottonseed does not change the total saturates plustrans content. The solids of the vegetable shortenings in the β form contained about 20% of 16:0, those in the β′ form 30% or more. The animal fat shortenings were mainly in the β form, their solids contained 30% or more of 16:0. C54 triglyceride content of the solids of β vegetable shortenings (calculated and IP-separated) was >45%, that of all animal fats was <25%. Solids of animal fat shortenings contain high levels of C52. The C54 triglycerides are β-tending and should be kept low in vegetable shortening. In the HMG the C54 should not exceed 30%. This can only be achieved by incorporation of a β′ hard fat, preferably palm hard fat. Animal fat, especially lard, crystallizes in the β form because the palmitic acid in the glyceride molecule is located in the 2-position, whereas those of vegetable fats are in the 1- and 3-position.     

Hydroxypropyl cellulose‐based esters for thermal energy storage by grafting with palmitic‐stearic binary acids

Fatty acid mixed esters (i.e., HPCMEs) with the onset phase change temperature around 32 °C were successfully synthesized by grafting palmitic‐stearic binary acids (PA‐SA) onto hydroxypropyl cellulose (HPC). The effects of reaction time, reaction temperature, initial ratio of reactants, and stirring speed on grafting ratio (GR) were explored. Characterizations by FTIR, ¹H NMR, DSC, and TGA were also performed to investigate their structure, thermal storage, and decomposition behavior. The results reveal that the prepared HPCMEs as thermoplastic copolymers exhibit high enthalpies, good repeatability, and enhanced thermal resistance properties. With the introduction of HPC rigid skeletons, gradual volatilization of fatty acids during use is well solved. The prepared HPCMEs thus are expected to have wide prospects for thermal energy storage owing to their proper phase change temperatures and excellent integrated performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44949.     

Simulation on hydrogen storage properties of metal‐organic frameworks Cu‐BTC at 77–298 K

In recent years, many researchers have studied on the hydrogen storage properties of metal‐organic frameworks (MOFs) by grand canonical Monte Carlo (GCMC) simulation. At present, the GCMC studies of Cu‐BTC (BTC: benzene‐1,3,5‐tricarboxylate) which is a prototypical metal‐organic framework mainly adopt the classical force fields, the simulation temperatures are mainly focus on 298 and 77 K, and most researchers did not consider the effects of quantum effects at low temperature. Therefore, we used the quantum effects to correct the classical force fields and the force fields with more accurate simulation results were used to simulate the hydrogen adsorption performances of Cu‐BTC in the temperature range of 77–298 K and the pressure range of 1–8 MPa at each temperature. The results show that the effects of quantum effects on the hydrogen storage of Cu‐BTC cannot be neglected and the corrected Dreiding force field can simulate hydrogen adsorption performances of Cu‐BTC more accurately at low temperature. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1383–1388, 2018     

Preparation and thermal energy storage properties of poly(n‐butyl methacrylate)/fatty acids composites as form‐stable phase change materials

This work is focused on the preparation, characterization, and determination of thermal energy storage properties of poly(n‐butyl methacrylate) (PnBMA)/fatty acid composites as form‐stable phase change material (PCM). In the composite materials, the fatty acids act as latent heat storage material whereas PnBMA serves as supporting material, which prevents the leakage of the melted fatty acids. The maximum encapsulation ratio for all fatty acids was found to be 40 wt%. The composites that do not allow PCM leakage in melted state were identified as form‐stable PCMs. The compatibility of fatty acids with PnBMA is investigated by optical microscopy (OM) and Fourier Transform Infrared (FT‐IR) spectroscopy. Thermal properties and thermal reliability of the form‐stable composite PCMs were determined using differential scanning calorimetry (DSC). DSC analysis revealed that the form‐stable composite PCMs had melting temperatures between 29.62°C and 53.73°C and latent heat values between 67.23 J/g and 87.34 J/g. Thermal stability of the composite PCMs was studied by thermal gravimetric (TG) analysis and the results indicated that the form‐stable PCMs had good thermal stability. In addition, thermal cycling test showed that the composite PCMs had good thermal reliability with respect to the changes in their thermal properties after accelerated 5,000 thermal cycling. On the basis of all results, it was also concluded that the prepared form‐stable composite PCMs had important potential for many thermal energy storage applications such as solar space heating of buildings by using wallboard, plasterboard or floors integrated with PCM. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Fatty acid composition and contents of trans monounsaturated fatty acids in frying fats, and in margarines and shortenings marketed in Denmark

This study examined trans monounsaturated fatty acid contents in all margarines and shortenings marketed in Denmark, and in frying fats used by the fast-food restaurants Burger King and McDonald’s. Trans C_18:1 content was 4.1±3.8% (g per 100 g fatty acids) in hard margarines, significantly higher than the content in soft margarines of 0.4±0.8%. Shortenings had an even higher content of trans C_18:1, 6.7±2.3%, than the hard margarines. Margarines and shortenings with high contents of long-chain fatty acids had about 20% total trans monoenoic of which close to 50% were made up of trans long-chain fatty acids. Both fast-food frying fats contained large amounts of trans C_18:1, 21.9±2.9% in Burger King and 16.6±0.4% in McDonald’s. In Denmark the per capita supply of trans C_18:1 from margarines and shortenings and frying fats has decreased steadily during recent years. The supply of trans C_18:1 from margarines and shortenings in the Danish diet is now 1.1 g per day.     

Healthier lipid combination as functional ingredient influencing sensory and technological properties of low‐fat frankfurters

Oil (healthier lipid combination of olive, linseed and fish oils)‐in‐water emulsions stabilized with different protein systems (prepared with sodium caseinate (SC), soy protein isolate (SPI) and microbial transglutaminase (MTG)) were used as pork backfat replacers in low‐fat frankfurters. Composition (proximate analysis and fatty acid profile), sensory analysis and technological (processing and purge losses, texture and colour) properties of frankfurters were analysed as affected by the type of oil‐in‐water emulsion and by chilling storage (2°C, 41 days). Frankfurters produced with oil combinations had lower levels of saturated fatty acids (SFA, 19.3%), similar levels of MUFA (46.9%) and higher levels of PUFA (33.6%) than control frankfurters (all pork fat) (39.3, 49.5 and 10.6%, respectively). PUFA/SFA and n‐6/n‐3 PUFA ratios in control sample were 0.27 and 9.27; in reformulated frankfurters the PUFA/SFA ratio was higher (1.7) and the n‐6/n‐3 PUFA ratio was lower (0.47). In general, frankfurters had good fat and water binding properties. Colour parameters were affected by formulation and storage time. Compared to control sample, frankfurters made with oil‐in‐water emulsions had higher (p<0.05) hardness, springiness and chewiness values. Emulsified oil stabilizing systems did not affect sensory characteristics of frankfurters, and all products were judged as acceptable.     

Effect of clay platelet dispersion as affected by the manufacturing techniques on thermal and mechanical properties of PMMA‐clay nanocomposites

In this work, the properties of Poly(methyl methacrylate) (PMMA)‐clay nanocomposites prepared by three different manufacturing techniques viz., solution mixing, melt mixing, and in‐situ bulk polymerization in presence of clay were studied. Morphological analysis revealed that the extent of intercalation and dispersion of the nanoclay were relatively higher in the in‐situ polymerized nanocomposites than those of solution and melt blended nanocomposites. Differential Scanning Calorimetric study indicated maximum increment in T_g of the PMMA in the in‐situ polymerized PMMA‐clay nanocomposites. Thermo gravimetric analysis showed improved thermal stability of PMMA in all the nanocomposites and the maximum improvement was for in‐situ polymerized nanocomposites. The storage moduli of all the nanocomposites were higher than the pure PMMA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Lipase‐catalyzed synthesis of structured lipids with fatty acids fractionated from saponified chicken fat and menhaden oil

In this study, free fatty acids (FFA) of chicken fat and menhaden oil, which were obtained by saponification, were dry‐fractionated and solvent fractionated. Using these fractionation processes, FFA fractions enriched in monounsaturated (MUFA) and polyunsaturated fatty acids were obtained. Chicken fat FFA fractions enriched in MUFA were modified further by lipase‐catalyzed esterification with the starting fat to produce structured lipids of high MUFA content.     

Influence of branching characteristics on thermal and mechanical properties of Ziegler–Natta and metallocene hexene linear low‐density polyethylene blends with low‐density polyethylene

The effect of the branch content (BC) and composition distribution (CD) of linear low‐density polyethylene (LLDPE) on the thermal and mechanical properties of its blends with LDPE were studied. All blends and pure resins were conditioned in a Haake PolyDrive blender at 190°C and in the presence of adequate amounts of antioxidant. Two metallocene LLDPEs (m‐LLDPE) and one Ziegler–Natta (ZN) hexene LLDPE were melt blended with the same LDPE. The effect of the BC was investigated by blending two hexene m‐LLDPEs of similar weight‐average molecular weights and molecular weight distributions but different BCs with the same LDPE. The effect of the CD was studied by using a ZN and an m‐LLDPE with similar weight‐average molecular weights, BCs, and comonomer type. Low‐BC m‐LLDPE blends showed separate crystallization whereas cocrystallization was observed in the high‐BC m‐LLDPE‐rich blends. However, ZN‐LLDPE/LDPE blends showed separate crystallization together with a third population of cocrystals. The influence of the crystallization behavior was reflected in the mechanical properties. The BC influenced the modulus, ultimate tensile strength, and toughness. The addition of a small amount of LDPE to a low‐BC m‐LLDPE resulted in a major improvement in the toughness, whereas the results for the high‐BC pair followed the additivity rule. ZN‐LLDPE blends with LDPE blends were found to be more compatible and exhibited superior mechanical properties compared to m‐LLDPE counterparts with the same weight‐average molecular weight and BC. All mechanical properties of ZN‐LLDPE blends follow the linear rule of mixtures. However, the CD had a stronger influence on the mechanical properties in comparison to the BC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2488–2498, 2005     

Hydrogen storage properties of B‐ and N‐doped microporous carbon

A B‐ and N‐doped microporous carbon has been synthesized via a substitution reaction. The obtained carbon exhibited much higher surface area than the previously reported B‐ and N‐doped carbon. The hydrogen storage measurements indicated that the B‐ and N‐doped microporous carbon had a 53% higher storage capacity than the carbon materials with similar surface areas. Furthermore, hydrogen storage via spillover was studied on Ru‐supported B‐ and N‐doped microporous carbon and a storage capacity of 1.2 wt % at 298 K and 10 MPa was obtained, showing an enhancement factor of 2.2. Ab initio molecular orbital calculations were also performed for the binding energies between the spiltover hydrogen atom and various sites on the doped carbon. The theoretical calculations can explain the experimental results well, which also shed light on the most favorable and possible sites with which the spiltover hydrogen atoms bind. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Development,rheological properties,and physical stability of d‐limonene‐in‐water emulsions formulated with copolymers as emulsifiers

This contribution reports the development of 30 wt % d ‐limonene‐in‐water emulsions formulated with a biopolymer (gellan gum) as stabilizer and prepared with a high‐pressure homogenizer. The role as emulsifiers of different ratios of amphiphilic copolymers (Atlas^TMG5000 and Atlox^TM4913) was assessed. The results indicated that the ratio of emulsifiers had significant effect on the physical stability, droplet size, viscoelasticity, and viscosity of these emulsions. The mean droplet diameters decreased as Atlas^TMG5000 concentration increased from 1 wt % to 3 wt %. The aging of emulsions resulted in an increase in the size of droplets for the emulsions containing high Atlox^TM4913 copolymer content. An increase of Atlas^TMG5000 enhanced both the G′ and G″ values and the viscosity providing higher stability to emulsions. Gellan gum caused in viscoelastic moduli weaker frequency dependence at the lower frequencies, according to the formation of a faint gel‐like matrix. All emulsions exhibited shear thinning flow properties that fitted the power‐law equation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43838.