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J. B. MICKLE, R. L. VON GUNTEN, AND R. D. MORRISON Departments of Dairying and Mathelnatics, Oklahoma State University, Stillwater

Milk fat was rearranged using selected times, temperatures, and catalyst concentrations, and the resulting fat was made into a semisolid product resembling butter. Hardness of the product was measured at 7-10 C and fomld to decrease with increased catalyst concentrations, but to increase with increased time. A 50 ± 5% reduction in hardness could generally be accomplished with catalyst concentrations of 1-2%. Statistical analysis indicated that catalyst concentration had more influence on hardness than did reaction time or temperature. This catalyst effect was related to the formation of diglycerides whose emulsifying properties partially explained the decreased butter hardness.

A report from this laboratory (8) indicated that butterlike spreads crystallized from interesterified (rearranged) nfilk fat were softer than similar spreads containing untreated milk fat. Riel's data (10) also indicated that rearrangement extended the plastic range of nfilk fat. Work by DeMan (4, 5) and Weihe (12), however, showed that rearranged milk fat was harder than untreated fat. Rearranged milk fat contained more high-melting-point glycerides (HMG) and formed smaller crystals upon solidification than did untreated control fats (5). When using sodium methoxide (NaOCH~) 2 as the catalyst, nmno- and diglycerides may be formed as a by-product of rearrangement. Braun (3), therefore, recommended low catalyst concentrations to avoid excessive fatty acid losses. The net effect of rearrangement on butter spreadability was obscure, particularly in view of the apparently conflicting data from different laboratories. It was thought, therefore, that additional information could be obtained if the effect of each reaction condition (time, temperature, and catalyst concentration) were evaluated. EXPERIMENTAL PROCEDURE I n the first series of trials, the effects of three reaction conditions (time, temperature, and catalyst) were evaluated with a random balance experimental design. Reaction times ranged from 5 to 55 min in 5-rain intervals,

Received for publication August 9, 1962. * Supported in part by funds from the American Dairy Association. ~Fisher Scientific Co., St. Louis, Missouri. 1357

temperatures ranged from 40 to 90, in 10 C increments, and catalyst (NaOCH~) concentrations from 0.5 to 5.0% of the fat. Of the 660 possible combinations of time, temperature, and catalyst, 31 were chosen at random, and 12 of these 31 combinations were duplicated at random. Milk fat for these trials was obtained from a single churning of unsalted, sweet cream butter stored at --15 C until used. As needed, portions of the butter were melted, then the dry milk fat decanted and filtered. The reaction was conducted under a nitrogen atmosphere, to avoid oxidative flavor deterioration. At the end of the treatment period the catalyst was inactivated with an excess of' acetic acid and the fat was washed three times with water. The fat was then neutralized with an 8% NaOH solution and deodorized with steam at 55-60 C and 150 mm Hg pressure for 8 to 12 hr (2). Water and NaCl were then added to the deodorized fat and the mixture which eontained 80% fat, 2% NaC1, and 18% H_oO was crystallized to a product resembling butter by cooling, with egitation, from 80 to 15-20 C in 4-5 rain. The special laboratory apparatus used has been described previously (S). The effect of the process on the finished product was evaluated by measuring hardness at 7-10 C with a consistency meter similar to the one described by Kapsalis et al. (6). The data were analyzed as a four-dimensional surface representing butter hardness as affected by each of the three reaction conditions. A second series of experiments was designed to compare the effects of selected reaction conditions on butter hardness and the ratios of mono-, di-, and triglycerides formed during rearrangement. The mono-, di-, and triglycerides

The equation f o r the f o u r dimensional surface was: Y = 533.i. The judges were asked to rank the samples according to taste preferences only. California.5. a f t e r which hardness increased with increased time..0 % Cofolysf FI6.Min.o. Time-.812 -6.164.. This equation could be used to calculate specific points ou the surface it represented or to determine the reaction conditions necessary to obtain a given hardness value.Mm. and C = catalyst concentration in p e r cent.and triglyceride fractious. Flavors of the butterlike products were evaluated by a taste panel composed of 11 women. .' ~ 300 m O O 5 ~ 0 420° 0 5. 1. 3[1CKLE. where Y = hardness of the butterlike product in grams. 215 ~ ~ 0 ~0 ~~ ~ Time .010Me + a An aerograph Hi-Fi Model 600.086T ~ + 13. This paired-comparison type design was repeated eight times and the pooled data were evaluated statistically.:ty. i ~ 5OO.. one containing rearranged milk f a t and the other.1 5 C until used ( l to 8 wk}. These minimum values formed a trough in the surface which extended diagonally across it. however.eee ~o bo 0 Time . VON G U N T E N .1358 J.t Time-Uin. the spreads became softer with increased time.437TC.o. T = reaction temperature in C.0.~es~-q H0. The column of the GLC instrument :~ was packed with 20% diethyleneglycol sueeinate on acid-washed 60-80 mesh chromosorb ~V and the saponified f a t t y acids were methylated before analysis. The fat was placed in a double-walled test tube cooled in a dry-ice ethanol bath at a rate of a p p r o x i m a t e l y 2 C / rain. until a mininmm hardness value was reached.I . 0.121MT . L. Each panel member ranked two coded samples at each tasting period. 0s~ co..0%. Surfaces representing the influence of rearrangement reaction time and temperature at selected catalyst concentrations on the hardness of butterlike products.. Wilkens Instrument & l~eseareh.2 ~ catalyst.oo "--'~--~ 600 800 ?00 600 Hord~ees-500 400 300 200 I00 60 50 40 30 20 1090 ~ Time. using the procedure of Smith {11). but were tempered at 7 to 10 C before taste evaluation. There was a general tendency for the butterlike spreads to become harder as the reaction time increased. B. ~. ~ZSULTS _a~D nlSe['SSIOX The data involved a four-dimensional surface. The surfaces were saddle-shaped with respect to time and temperature and their shape was modified somewhat by changes in the catalyst concentration. M = reaction time in minutes. I n general. o 0 o ~o'°S°'d"**s-~ . AND R.063M ~ -0.$.155T -. and gas-liquid chromatography (GLC) was used to analyze the di. M O R R I S O N were separated by Florisil colunm chromatography. The samples were stored at .1 C) were obtained with a thermistor attached to a Wheatstone bridge-galvanometer circuit. a control.. containing untreated milk fat.. parts of which are shown in a series of three-dimensional drawings ( F i g u r e 1). These surfaces indicated that the butterlike spreads became softer as catalyst concentrations increased within the range of 0.Nin ~^ =^ "1 30 20 I0 "--]--'--] 800 1 ~...~=_o 1 T '°° ~ . R. ~'Ieasurements of fat temperatures (aecurate to 0. q Time-ui. D. Cooling curves were determined on 20-ml aliquots of rearranged and untreated samples of milk fat.242M -t. Walnut Creek. A t the higher catalyst concentrations and lower temperatures.538C ~ + 0.d.d. hardness reductions of 45-55% were obtained with 1 .1.197C q. .5 to 5. Inc.

REARRANGEMENT OF M I L K F A T 1359 TABLE 1 Influence of time. Statistical analysis of the data (Table 1) indicated that the effects of time.05). which indicated that the reaction was affected by combinations of variables in addition to those measured (i. complex eurvilinear effects. The catalyst effect. 5) and attributed to the formation of HMG.). The lack-of-fit term included all those combinations of variables which had not been analyzed individually. In this case.5 40 60 80 18 2 170.e been precise only for the particular points they represented. that when the catalyst concentration was increased 0.157 13.408 40.380 1. 12).240 % Softer than control . 0 1 ) linear interaction between time and temperature could probably be explained by the fact that these variables sometimes affected hardness in different directions. and catalyst concentration on a rearrangement reaction as it affects the hardness of butterlike products Analysis of variance Source d.5% or more.8 b 7.. since it represented the sum of all the individual variations.. The changes in the fat which accompanied (and perhaps caused) the changes in hardness were of interest. The total experimental error. The increase of hardness with time had previously been studied by DeMan (4. When 0.320 53. though.6 ~ 4. a reasonable value for a design of this type. individual experimental variations were snmll: the average difference between hardness measurements. When 2. The relative size of the F values indicated that of the three factors studied the catalyst concentration had the largest single influence on hardness..2%. ~'P ~ 0. M. a softer butter was produced at nearly all times and temperatures. temperature. 60 % Glyceride composition of fat Tri94 93 Di5 6 Mono1 1 Butter hardness ( g ) 1.e. would ha~. In most eases.. The effect of catalyst concentration appeared to be independent of time and temperature since linear interactions between this variable and the other two were not statistically significant (P > ..2 ~ 4. This term was significant (P ( .0 b Mean 1 Linear effects Time 1 Temperature 1 Catalyst 1 Quandratic effects Time 1 Temperature ] Catalyst 1 Linear interactions Time × temperature 1 Time X catalyst 1 Temperature X catalyst 1 Lack of fit 22 Error (duplicates) 11 " P ~ 0. Similar observations were previously reported from this laborato~' (8). the general tren~lg determined by. the over-all coefficient of variation was 19.2 0. however.05..8 ~ 6.0 " ~ 11.f. 88 % Catalyst 0 0.467 1.05). was about 3%.957 11. the increase in diglyceride content of the rearranged fat was negligible. The catalyst effect could possibly have been explained by the formation of diglyeerides during the reaction and it was of interest to relate the amounts of these compounds formed during rearrangement to changes in hardness.672 ] 2. In this work. presents typical data obtained under different reaction conditions.893 2. the butter made from the rearranged fat was about 10% softer than the control sample which contained untreated fat. 40 Time (~*~b~utes) . for example.067 640. and catalyst each were statistically significant (P < . since hardness increased with time at low catalyst concentrations.727 5.5 19. These findings of this work agree with the data of others (4.01.5% . The random-balance experimental design was an exploratory technique which determined the general shape of this surface. 5.173. _~[ore precise predictions of hardness could have been obtained by repeating portions of the experiment and changing only one variable at a time.. was larger. On the other hand.982 ]7. The statistically significant (P ( . The effect of temperature was more important than time. the random-balance design should be valid under most circumstances. time × temperature × catalyst. 0 1 ) .. 10 Control sample containing untreated milk fat.S. Table 2 TABLE 2 Glyceride comp(~sition and hardness of butterlike products containing rearranged and untreated milk fats Reaction conditions Control ~ Experimental 2. however.8 b 234. temperature. was so large in relation to the effects of time and temperature.. 3.. etc.573 32.5 15.1 Temperature ( C ) .1% catalyst was used and the reaction was conducted at 40 C for I hr.528 19. Such data.

1360 J B. an effort was made to determine whether the emulsifying properties of the diglyeerides produced would account for the reduction in hardness which accompanied the increased diglyceride content. The product resulting from rearrangement had an intense metallic flavor. To do this.5% catalyst contained more HMG than did the control. Melting points of simple diglycerides have been reported to be higher than their corresponding triglycerides (2). on the availability of suitable equipment.. I n eonunereial practice. the rearrangement reaction appeared to have been random in this ease and differences in fatty acid composition of the glyee14des resulting from rearrangement did not appear to have been the cause for the softer butter. among other things. Wihnington. the effect of added enmlsifiers was tested. When this 76% reduction was compared to the 36% caused by 15% Atmos 150. Thus. Atlas Powder Co. MICKIA~. The feasibility of rearrangement as a commercial practice will depend. Atlas Powder Co. a 50% reduction in hardness would require more than 1% of added emulsifier. Wihnington. thus.and diglyeerides. Atlas Powder Co. This increase in HMG was contrary to what one might have expected. a liquid at 21 C. The cooling curves also indicated that the sample rearranged with 2.and diglyeerides. VON G U N T E N . the Tween 21 was not as effective in reducing hardness as were the natural glyeerides formed during rearrangement. These data indicated that the hardness of some nfilk fats would have to be reduced more than 50% to produce butter with a desirable spreadability over a wide temperature range. TABLE 3 Hardness of butter containing added emulsifiers Emulsifier Description Atmos 150 ~ Butter hardness (% (%) 0 10 15 0 10 15 (g) 1. The Atmos and Tween added to some of the fat were not primarily diglyeerides and this might have accounted for part of the difference when the effects of these substances were compared to the effects of the diglycerides formed during rearrangement. GLC analysis of the control fats and the diglycerides from rearranged fats indicated fatty acid compositions were the same for both ~Mono. When diglycerides were produced by rearrangement fatty acids were released--many of them as sodimn soaps. The crystallization of this fraction began at a temperature 2 C higher than that of the control sample. AND R.. 5). Delaware. crystalline at 21C. R.. This latter enmlsifier was liquid at room temperature. since it has been shown that an increase in ttMG is sometimes associated with harder fat (4. Kapsalis et al. using two conunereially available products.630 1. but this flavor was removed by the refining processes employed in this study.1% catalyst.290 760 310 softer) 35 36 41 76 Tween 21 b Edible mono. the increase in tI3IG might have been accounted for by the increased diglyeeride content of the rearranged fat. This reduction in hardness was accompanied by an increase in the diglyeeride content of the rearranged fat. The addition of 15% Tween 21 ' caused a 76% reduction in the hardness of the butter. Cooling curves indicated no difference between the HMG content of the control fat and the rearranged fat when using 0. Delaware.060 1. Wihnington. fats. (6) and Riel (9) have published data which indicated desirable ranges of spreadability and hardness. the butter made from rearranged fat was 88% softer than the control. a level which might cause undesirable flavors in the butter (7).. Delaware. it appeared that the physical characteristics or chemical composition of the emulsifier nmst have had a substantial effect upon the hardness of the butter. b Polyoxyethylene sorbitan monolaurate. I). However. The taste panel found no statis- . Polyoxyethylene sorbitan monolaurate. Such a reduction in hardness could be accomplished by adding commercially available enmlsifiers to the butter.050 1. Another consideration of commercial importance is the taste of the final product. I. These values all were similar to those reported by Smith (11). this saponifieation could be prevented by adding glycerol to the reaction mixture or the fatty acids could be recovered per se by one of several available procedures (2).. Delaware. On the other hand. the addition of 15% Tween 21 did not cause as great a reduction in hardness (Table 3) as had 12% of additional natural diglyeerides (Table 2). Wilmingtou. Thus. When 10 or 15% Atmos 150' was added. M O R R I S O N catalyst was used under the same time and temperature conditions. there was a linfit (about 35%) to the decrease in hardness which could be affected by the addition of enmlsifier (Table 3). Therefore. whereas the Atmos 150 was solid. Atlas Chenfieal Co.

. KRISTOFFERSEN. (3) BRAUN. Inc. 1961. J.. AND GOULD.A. (12) WEmE. Dairy Sci. B. The Consistency of Butter as Determined by Mechanical and Consumer Panel Evaluation Methods. M. 43: 1560. E. W e i h e also has r e p o r t e d acceptable flavor in r e a r r a n g e d milk f a t a f t e r it was refined (12). J. Sta.. 44: 944. Dairy Research. J. 1961. Am. J.~ILEY. Dairy Sci. M. Specifieatio~s for the Spreadability of Butter. AND BETSCttEg. J. even a f t e r 8 wk of storage. II. Inc. 1961. J. W. Changing the Molecular Structure of Milk F a t as a Means of Improving the Spreadability of Butter. Q. 1950. II. (11) SMITH. Dairy Research. T. 1961.. Dairy Sci. H. I. (8) MICKLE.REARRANGEMENT OF MILK FAT tically significant differences ( P < 0.. J. J. J. Barbara Chandler.. A.05) between the samples containing refined r e a r r a n g e d milk f a t and control samples. Melting and Solidification of Fats. 1960.. L. (4) DEMAN. Soc. Laboratory and Plant Churnings. Dairy Sci. 5. (7) KAPSALIS. Oklahoma Agr. J. Bull.. 1951. Effect of Chemical Additives on the Spreading Quality of Butter. New York. 46: 107. REFERENCES (1) B. A. J. Interscience Publ. Betty Christians. I.. I. W. 1960. J. Influence of Chemical Modification. Quantitative F a t t y Acid Anal)-sis of Milk F a t by Gas-Liquid Chromatography. and Mary Leidigh.. J. 44: 607. T-83. J. E. Dairy Sci. G.. Dilatometric Behavior and Other Properties of Modified Milk Fats. GOULD. 28: 117. Oil Chem.. R. Interscienee Publ. who helped prepare and analyze the samples. KglSTOFFERSE~. (10) RIEL. (2) BAILEY. T. J. (6) KAPSALIS. (9) R mL. D. Industrial Oil and Fat Products. Some Factors Influencing Crystal- 1361 lization. R.. 44: 1168. 28: 81. 1963. I. ACKNOWLEDG~IENTS The authors are indebted to tIazel Baker.. Effect of Chemical Additives on the Spreading Quality of Butter. Physical Properties of Milk I~at. R. Dairy Sci.. Interesterified Butteroi]. New York. G. Expt. Mary Malkus. Interesterification of Edible Oils. 1960.. J. 1~. 1961. BETSCHER. 43: 1224. (5) DEMAN. Physical Properties of Milk Fat. . A. 1960. 2nd ed. 37: 598. J.