Hard butters and confectionery coatings

The art on confectionery coatings and hard butters is reviewed showing the evolution and acceptability of such products over the years. The various types of hard butters are identified, and their application in confectionery coatings is indicated. The practices and the areas of application for the different products are discussed as well as the raw materials used to produce the confectionery fats. Raw material cost of chocolate and hard butters is projected over the years to demonstrate the advantages of hard butters for confectionery coatings.     

Manufactured hard butters

The physical characteristics of various commercial hard butters are compared by determining their solid contents (dilatometrically) and melting thermograms (DSC). For most applications in the confectionery industry, hard butters manufactured by the hydrogenation and interesterification of fats and oils offer economic advantages over those obtained by the fractionation of fats. Condensed from the paper presented at the AOCS Meeting, May 1977 in New York.     

Confectionery fats from palm oil and lauric oil

In the search for economical cocoa butter alternatives, palm and lauric oils have emerged as important source oils in the development of hard butters. Based on the method presented for categorizing hard butters, the lauric oils, primarily palm kernel and coconut, can be modified by interesterification and hydrogenated to yield lauric cocoa butter substitutes (CBS) which are both good eating and inexpensive. Fractionation, although adding to the cost of production, can provide lauric hard butter with eating qualities virtually identical to cocoa butter. Unfortunately, one factor identified with the lauric oils is their very low tolerance for cocoa butter. Palm oil, on the other hand, has been identified as a valuable component in all types of cocoa butter alternatives. It is a source of symmetrical triglycerides vital in the formulation of a cocoa butter equivalent (CBE). It can be hydrogenated or hydrogenated and fractionated to yield hard butters with a limited degree of compatibility with cocoa butter, allowing some chocolate liquor to be included in a coating for flavor enhancement. Palm oil is used with lauric oils as a minor component in interesterified lauric hard butters, as well as functioning as a crystal promoter in coatings formulated with a fractionated lauric CBS. While palm oil’s importance and flexibility have been duly noted, some important concerns remain from a market perspective. The fact that the CBE fats are very expensive suggests they offer limited cost savings compared to cocoa butter. The potential for CBE products is still questionable in those countries where chocolate labeling standards preclude the use of vegetable fats other than cocoa butter. The nonlauric CBS products, while cheaper than the CBE types and able to tolerate limited levels of cocoa butter, do not exhibit the level of eating quality characteristics present in the lauric hard butters. Some challenges remain for today’s oil chemists. An economical nonlauric CBS, made predominantly from palm oil, possessing the eating quality of a fractionated lauric CBS and exhibiting good compatibility with cocoa butter would be met with considerable interest by the chocolate and confectionery industries. As for the lauric oils, it would seem reasonable to assume that greater cocoa butter compatibility, if attainable, could enhance their potential for gaining even greater acceptance by confectionery manufacturers currently using pure chocolate. As for the CBE products, the major issue is cost. If the cost of a CBE could be reduced to a level which would allow a CBE to compete with the nonlauric and lauric cocoa butter substitutes, a major advancement in the evolution of cocoa butter alternative fats will have been achieved.     

Lipid and hardness characteristics of cocoa butters from different geographic regions

Twenty-four commercially pressed cocoa butters and 39 laboratory solvent extracted cocoa butters were evaluated. A rapid method using differential scanning calorimetry (DSC) was used to evaluate the hardness of small quantities of cocoa butter. In the DSC thermogram of a quenched sample, the percentage area under the polymorph II endotherm had a positive correlation (r=0.74) with the mechanical hardness. Soft cocoa butters were characterized by high POO, SOO content (P=palmitic acid, O=oleic acid, S=stearic acid), high iodine value, low percentage, area under the polymorph II endotherm from the DSC scanning, and low SOS. Hard cocoa butters displayed opposite characteristics. In general, South American cocoa butters were the softest and had a 37.03 iodine value, a total of 9.1% POO and SOO, and a 26.4% area under the polymorph II endotherm. Cocoa butters from Asia and Oceania were the hardest and had a 34.74 iodine value, a total of 4.1% POO and SOO, and a 35.65% area under the polymorph II endotherm. North and Central American and African cocoa butters were intermediate in hardness characteristics.     

Comprehensive Triacylglycerol Characterization of Oils and Butters of 15 Amazonian Oleaginous Species by ESI‐HRMS/MS and Comparison with Common Edible Oils and Fats

The Amazon rain forest encompasses an extraordinary source of vegetable oils with many applications, especially for food, pharmaceutical and cosmetics industries. In this work, the main composition of fifteen Amazonian oils and butters are investigated via gas chromatography‐mass spectrometry (GC‐MS) and electrospray ionization high resolution mass spectrometry (ESI‐HRMS). Triacylglycerols (TAG) are characterized by their fragmentation spectra and comparison with the LIPID MAPS database, resulting in a detailed compendium of TAG composition of these samples. Over 70 different TAG are putatively annotated per sample and the occurrence of isomers is remarkable, showing that TAG complexity in these samples is considerably higher than ever reported. The TAG composition of the Amazonian samples are also statistically evaluated using principal component analysis (PCA) for comparison to common edible oils such as soybean, corn, coconut, and olive oil. Some tendencies of grouping are observed: butters with medium chain fatty acids (FA); butters with high oleic FA; and oils with high oleic and high linoleic FA contents. This study provided profiles that ensure Amazonian oils and butters authenticity, quality and also aids in understanding their properties and the best applications for each. Practical Applications: It is expected that this comprehensive set of data on the TAG composition of Amazonian oils and butters will help guide the use and applications of these products, providing consumers with the best benefits from a nutritional perspective. Moreover, adulterations could be more easily detected when a database is available, since the chemical composition of certified samples is investigated in this work. Ultimately, this study can encourage the sustainable production and applications of Amazonian oils and appropriate use of Amazon rain forest resources.     

Triterpene alcohols, 4-methylsterols and 4-desmethylsterols of sal and illipe butters

Four 4-desmethylsterols, four 4-methylsterols and eight triterpene alcohols were isolated from sal and illipe butters and identified by¹H nuclear magnetic resonance and mass spectrometry. In addition to some components which had been shown to be present in these fats, several triterpene alcohols and one 4-methylsterol are described for the first time in these fats. An analytical method for detection of sal or illipe butters in foodstuffs is suggested.     

A Simple and Direct Procedure for the Evaluation of Triglyceride Composition of Cocoa Butters by High Performance Liquid Chromatography - A Comparison with the Existing TLC-GC Method

A high performance liquid chromatography (HPLC) method for the separation of triglycerides in cocoa butters at nanogram sensitivity is described. This procedure is based on UV detection at 220 nm. This study demonstrates the feasibility of using UV detection system for the quantitation of triglycerides employing a chromatographic separation system coupled with stop flow technique. HPLC analysis of triglycerides from various cocoa butters compared well with values obtained by existing TLC-GC method. This appears to represent the first report to describe the quantitative analysis of triglycerides employing short wavelength UV detection. The rapid quantitative analysis of triglycerides by HPL C holds promise in the qualitative evaluation of cocoa butters.     

Evaluation of the differential scanning calorimetric method for fat solids

Denison et al. (1) recently reported a method for measuring the per cent solids in fats using the Differential Scanning Calorimeter (DSC). The present work evaluates that method using the Perkin Elmer DSC-1, compares it with nuclear magnetic resonance (NMR) and dilatation methods, and extends it to hard butters. Although the method gave excellent interlaboratory agreement with soft fats, extension to hard fats led to greater experimental variance than SFI. The DSC method provides greater speed (one hour elapsed time) and additional information (thermal “fingerprint” of the fat). Thus, the DSC determination of fat solids overall compares favorably with the NMR method, as well as the SFI dilatation method. The DSC method is readily adaptable to quality control use. Presented at the AOCS Meeting, New Orleans, May, 1967. Now Mrs. K. Saunders.     

化妆品用天然植物油脂

天然油脂产量的不断增加及其广泛的应用价值使其变得越来越重要。介绍了不同科属油脂的命名,传统用法、物理化学性质及其在化妆品中的应用。     

Determination of the solid fat content of hard confectionery butters

A method is described for the determination of the solid fat content in hard confectionery butters of the nonstabilized type, e.g., palm kernel sterine. The method is based on the technique of low-resolution pulsed nuclear magnetic resonance (pNMR) by means of which the solid fat content of a fat sample can be calculated directly from the relative intensity of signals arising from protons in both the liquid and solid phases. A measuring procedure is reported, based on the use of the Bruker Minispec p20i low-resolution pNMR spectrometer, and attention is drawn to the stabilization pretreatment to which the fat samples need to be subjected prior to measurement in the pNMR instrument. The entire procedure is straightforward to operate and ideally suited to the measurement of large numbers of samples. The relationship between the solids content (N-value) and dilatation (D-value) is discussed and an interconversion table is given. The accuracy and reproducibility of the method are indicated.     

Cocoa butter extenders from Kokum (Garcinia indica) and Phulwara (Madhuca butyracea) butter

Cocoa butter extenders, suitable for use in chocolate and confectionery, were prepared from Kokum fat and a Phulwara butter fraction. The latter fraction was prepared from Phulwara butter by two-stage dry fractionation and blended with Kokum fat in selected proportions to obtain a series of hard butters with different melting profiles. The blends with higher proportions of Kokum fat were harder and hence may find application in warm climates. The blends with higher proportions of Kokum fat were harder and hence may find application in warm climates. The blends had solidification properties, fatty acid and triacylglycerol compositions similar to those of cocoa butter. In addition, they had narrow melting ranges like cocoa butter, and they were compatible with cocoa butter and have tolerance toward milk fat.     

DSC-Thermoanalyse und Kinetik der Kristallisation von Kakaobutter

DSC-Thermal Analysis and Kinetics of Cocoa Butter Crystallization A DSC method for isothermal crystallization of cocoa butter is described. The crystallization curves may be linearized according to the empirical Avrami equation. From the resulting Avrami plots the rate constant of crystallization may be calculated. This method gives valuable results about the specific crystallization tendency of cocoa butters of different origins and about temperature influence on crystallization times. The method seems to be useful for quality control of cocoa butters and for process control during the tempering step of the industrial chocolate production.     

自然界的美肤礼物--橄榄油

橄榄油不仅是最值得期待的营养油,也是独特的化妆品成分的来源。该成分可以用来制造一系列的以橄榄油为基础的化妆品。介绍了新的活性成分：润肤剂、牛油和石蜡、胶凝剂以及表面活性剂和乳化剂。它们的性质决定了它们可用于护肤品、护发品、个人护理和装饰性化妆品。     

Crystallization of Cocoa Butter in Cocoa Powder

Cocoa powder quality is determined by its color, flavor, dispersion, and flow properties, which can be controlled via tempering. Design of a cocoa powder tempering profile, however, requires that the mechanism of cocoa butter crystallization in cocoa powder be fully understood. Low-fat (8–12%) and high-fat (20–24%) cocoas were sourced from two commercial manufacturers at varying degrees of alkalization and compared with two commercial cocoa butters. Unrefined paired cocoa powders and cocoa butters sampled from the hydraulic press were also evaluated. Isothermal crystallization kinetics and polymorphism of cocoa powders and cocoa butters were compared at 18, 21, and 24 °C using a direct time-domain nuclear magnetic resonance method, differential scanning calorimetry, and x-ray diffraction. Crystallization was also studied under dynamic tumbling conditions. It was found that cocoa butter in cocoa powder was nucleated by the cocoa powder matrix and transitioned to higher-stability polymorphs more rapidly than bulk cocoa butters. High-fat cocoas also exhibited enhanced crystallization kinetics relative to low-fat cocoas, showing that differences in the cocoa microstructure may influence crystallization behavior. Notably, alkalization did not significantly affect the crystallization behavior of most cocoa powders. Finally, it was found that tumbling conditions led to crystallization of βV and that caking, especially of high-fat cocoas, could be reduced by a static low-temperature hold step prior to tumbling. Overall, these results demonstrated that crystallization of cocoa butter in cocoa powder is influenced both by the intrinsic attributes of the cocoa powder as well as the conditions of the tempering process.     

Phospholipid concentration in cocoa butter and its relationship to viscosity in dark chocolate

Fats extracted from chocolate liquor with a polar solvent, chloroform-methanol, was found to be 0.65% phospholipid. The evidence indicates that the phospholipids are associated primarily with the nonfat solids since concentrations were much lower in fat recovered with nonpolar solvents, hydraulic pressing and centrifugation. Seven of the 11 commercial cocoa butters analyzed had phospholipid concentrations between 0.05% and 0.13%. The highest concentration found was 0.57%. The reduction in viscosity caused by the addition of these butters, 14% by weight, to chocolate was related to the phospholipid concentration in cocoa butter. The higher the phospholipid level, the greater was the viscosity-reducing effect of the cocoa butter. Paper No. 3518, Journal Series of the Pennsylvania Agricultural Experiment Station.     

Dynamic crystallization of cocoa butter. I. characterization of simple lipids in rapid- and slow-nucleating cocoa butters and their seed crystals

Six cocoa butters with different crystallization induction times and their seed crystals were analyzed for simple lipid composition. The rapid-nucleating cocoa butter samples had higher concentrations of 1-palmitoyl-2-oleoyl-3-stearoylglycerol and 1,3-stearoyl-2-oleoylglycerol (SOS), and lower concentrations of the diunsaturated triacylglycerols, 1-palmitoyl-2,3-oleoylglycerol and 1-stearoyl-2,3-oleoylglycerol, as well as higher stearic acid concentrations within their diacylglycerol fractions when compared to the slow-nucleating samples. At the early stages of crystallization, under agitation conditions at 26.5°C, cocoa butters solidified into two fractions, high-melting and low-melting. The low-melting fractions were composed of polymorphs IV and V of cocoa butter, as indicated by the onset melting temperatures of the endotherms from differential scanning calorimetry. The high-melting fractions, which had wide melting ranges, had peak maxima of 38.5–52.2°C. Seed crystals isolated at the early stage of crystallization were characterized by high concentrations of complex lipids, saturated triacylglycerols, saturated fatty acid-rich diacylglycerols, and monoacylglycerols. The rapid-nucleating seed crystals had higher concentrations of SOS when compared to their respective cocoa butters. The slow-nucleating seed crystals did not exhibit this characteristic.     

Palm Kernel and coconut oils: Analytical characteristics,process technology and uses

Palm kernel and coconut oils are the most used of the lauric acid group of oils. The characteristic of this group is their high content of saturated acids, lauric and myristic, and it is from this feature that their principal uses are derived. Due to their triglyceride composition, both oils have steep melting curves and melt below body temperature. Their low degree of unsaturation gives them high oxidative stability. As a result of these properties they are found widely used as hard butters and in vegetable fat ice-creams, coffee whiteners and similar products. Their use in margarine gives that product an attractive coolness in the mouth. Coconut oil is also used extensively as a raw material for soaps and detergents and as a body oil. The oils are susceptible to hydrolytic splitting and to trace metal catalyzed oxidation. They are particularly affected by contamination with other oils which produce either reduced oxidative stability or, when the contaminant is high melting, an unacceptable palate cling. Refining is normally done with caustic soda solutions and refining conditions are chosen to minimize neutral oil losses due to saponification. Physical refining is also practised and is particularly useful for treating palm kernel oils with high free fatty acid content. To improve their quality and applicability for several uses, both oils are hydrogenated, fractionated and interesterified in various combinations. Fractionation is done either by dry “pressing” or with the assistance of detergents or solvents, the highest quality products being obtained using solvents. The relatively high solubility of the fatty acids can result in effluent problems.     

Comparision of acidic and basic volatile compounds of cocoa butters from roasted and unroasted cocoa beans

A total of nine acidic and 83 basic compounds was identified in the roasted and unroasted cocoa butter samples. Forty seven of the compounds identified are being reported for the first time in cocoa. The higher concentration of short chain fatty acids in the unroasted cocoa butter is responsible for its acidic aroma characteristics. The roasted cocoa butter generally contained greater numbers and higher concentrations of compounds whose formations would be favored by thermal processing. These compounds included pyrazines, thiazoles, oxazoles and pyridines. The aromas of many of these compounds are characteristic of the aroma differences between the two cocoa butters and contribute to the cocoa aroma of roasted cocoa butter.     

Effect of temperature on recrystallization behavior of cocoa butter

Crystallization of cocoa butter in the β phase directly from the melt is only possible by employing the memory effect of cocoa butter. Cocoa butter crystallized in the β phase, heated to the so-called maximal temperature (just above its melting end point), recrystallizes in the β phase after cooling to a crystallization temperature. The influence of the maximal and crystallization temperatures on the recrystallization behavior has been investigated for two cocoa butters. Rapid-starting recrystallization into the β(VI) phase and slow-starting recrystallization into the β(V) have been observed. It is concluded that rapid-starting recrystallization is induced by high-melting 1,3-distearoyl-2-oleoyl-glycerol (SOS)-rich crystals. The two β phases were identified by X-ray powder diffraction and melting ranges. However, the X-ray powder diffraction patterns for the β phases depended on the composition of the cocoa butter and on the crystallization method used. Therefore, it was not possible to take any particular β(VI) X-ray powder diffraction pattern as a standard for the β(VI) phase of all cocoa butters.     

Portable Infrared Spectrometer to Characterize and Differentiate Between Organic and Conventional Bovine Butter

The performance of a portable infrared system combined with pattern recognition to discriminate between organically and conventionally produced bovine butter samples as well as to predict the levels of conjugated linoleic acid (CLA) were evaluated. Sixty butter (27 organic and 33 conventional) samples were used in this study. Bovine butter–fat were applied onto an attenuated total reflectance infrared (ATR‐IR) accessory equipped with a five‐bounce ZnSe crystal set at 65 °C for spectral collection. In addition, ATR‐IR spectra of bovine butter were directly collected at room temperature to avoid phase separation. The fatty acid profile and the levels of CLA were determined using reference FAME‐GC‐FID analysis. SIMCA models showed well separated clusters that discriminated between organic and conventional bovine butters due to C=C trans bending out of the plane vibration modes band at 967 cm^?1. Additionally, strong PLSR models were developed to predict CLA levels using butter–fat and bovine butter spectra with SEP of 0.05 % and RPD of 4.7, indicating that the models are suitable for quality control applications. Portable IR technology offers the ability for “in situ” analysis of butters that is much less time consuming than current analytical practices for authentication and quality control efforts by the industry.