Copyright is owned by the Author of the thesis. Permission is given for a copy to be downloaded by an individual for the purpose of research and private study only. The thesis may not be reproduced elsewhere without the permission of the Author.

PROMOTI:ON OF BROWNING m TEE DEVELC>BU!NT

OF NEW DAIRY HWDUC!.IS

A niesi.s

Presented to

the Faoul ty of the Department of Food Science and Biotechnology

Massey University

In Partial Ful.:f'ilment

of the Requirements for the Degree

Jlaster of Food Technology in Food Processing

by

Wa.rwi.ok David Ward

July 1967

"It is not enough to know; -we must turn 'tlhat we

know to account. It is not enough to mil; we

must do. 11

- Goethe

ACKNOWLEDGEKENTS

'.I.he author wishes to thank the supervising camni ttee o£ Mr. H. A. L. Morris

(Convenor), Dr. E. L. Richard.a, and Dr. R. M:. Dolby. Sincere appreciation and

grati tud.e go to Mr. H. A. L. Morris for his encouragement, and particularly for

his keen interest in this study. His practical experience, willingness to talce

part in lengthy discussions, and help in the planning and presentation of this

thesis has proved to be invaluable.

'.Ihanks are due to the Dairy Prod.uc ti on and Marketing Board and the San­

itarium Health Food Canpany for financial assistance.

Special thanks to Miss D. Scott for the excellent photography and printing

of the graphs and photographs, and also to Miss c. Ki tohell f'or her hand in the

photographs, studio work, and fixing of the graphs and photographs.

For much frui tt'ul help and discussion, the author is indebted to the

willingness o£ Mr. J. G. Clarke, Dr. W. B. Sanderson, and Kr. D. Box, of the

New l.ealand Dairy Research Institute.

To the l.mtiring help and patience ofhis sister, Miss :M. Ward, in the prep­

aration and typing of this thesis the author is gratefully indebted for the final

presentati.cn. 'lhe author also wishes to thank his family and close friends for

their encouragement, and for their help in so many ways to make this work an

enjoyable experience.

nie assistance and interest of numerous other people "tilo have contributed

in many eya is also muoh appreciated and baa made the "WOrk on this thesis that

muoh more interesting.

TABLE OF CONTEN'IS

PART A. BASIC SWDIES ON 'IHE BROWNING OF MIIK SOIIDS

SECTION I. A REVIEW OF PREVIOUS RESEARCH INTO 'IHE BROWNING OF

DAIRY PRODOO'IS • • • • • • • • • • • • • •

I. Introduoti on • • • • • • • • • • • • • •

II. Reao tan ts and Jleohani sm • • • • • • .. • • •

III. :Ehencmena Associated with Browning • • • • • • • •

A. Ccmpound fomation • • • • • • • • • •

B. Reducing substa.noes • • • • • • • • • • •

o. Strecker degradation • • • • • • • • • • •

D. loss of nutritive value • • • • • • • • • •

E. !Dss of protein solubility • • • • • • • • •

IV. Caramelized Flavour • ! • • • • • • • • • • •

v. Factors Atteoting the Bate of the Browning Reao ti on • •

VI. Salient Features of Previous Work • • • • • • • •

SECTION II. DEVEIDBrnNT OF A KEMOD FOR MEASURING '1HE DEGREE OF

BROWNING IN A DAIRY PRODUCT SISTml • • • • • • • •

I. Chemical Jlethods • • • • • • • • • • • • • •

A. Literature review • • • • • • • • • • • •

B. Selection of a method for studies an adva:noed browning

in sweetened condensed milk • • • • • • • •

n. Development of a Method. of Measuring Product Colour as an

Index to the Progress and Rate of the Browning Reaction •

PAGE

1

2

3

8

9

10

10

11

11

13

15

17

19

20

20

24

28

PAGE

A. Li. tera ture review • • • • • • • • • • •

B. Development of a method tor the measurement of

browning - based an product colour • • • • • •

o. A new method of plotting reflectance results to

d.etel11line the rate of' browning • • • • • • •

III. Correlation Between Chemical (HMF) and :Ehysical (Reflectance)

.Methods for the lleasurement of the Rate of Browning • •

IV. Summary • • • • • • • • • • • • • • • . . .

SECTIOO" III. A BASIC STUDY OF FACTOBS INFUJENCDlg. BROWNING m SWEETENED

I.

II.

III.

CONDENSED MILK • • • • • • • • • • • • • •

Studies on the Effect of Temperature on the Development

of Dairy Caramel • • • • • • • • • • • •

Study of the Effect of Moisture Concentration on the Rate

of' Browning of Sweetened Condensed Milk • • • • • •

A. Effect of moisture concentration on browning in

sweetened condensed milk • • • • • • • • •

B. Effect of moisture content on broming in a model

system oonta1 ning skim milk pawder • • • • • •

c. A proposed theory to explain the effect of moisture

oonoentratiai on browning in liquid systems - arising

out of the previous study of sweetene~ condensed milk

and glycerol-milk powder systems • • • • • •

D. Changes in moisture concentration during browning of

sweetened condensed milk • • • • • • • • •

Studies an the Ef:feot of pH on Browning in Sweetened

Condensed lti.lk • • • • • • • • • • • • • •

28

29

32

36

39

41

1+3

49

49

51

55

58

61

PAGE

IV. Canparisan of the E:fteot of Two Sugars on the Brcnming

Reaction in Concentrated llilk • • • • • • • • 66

A. Effect on the rate of browning • • • • • • • 69 B. Rate of solubility decrease • • • • • • • • 69

v. Summary of Factors Influencing Browning in Sweetened

Condensed Milk • • • • • • • • • • • • • • 70

PART B. DEVEU>PlmlT OF NEf PRODUCTS BY PROMOTING BROWNING m MIIK SOLIDS

SECTICN IV. S'IDDIES ON 'lHE DEVEIDFMENT OF A SWEETENED CARAMELIZED DAIRY

SffiEAD • • • • • • • • • • • • • • • • 74

I. In trod.uo ti on • • • • • • • • • • • • 75

II. Flavour Development • • • • • • • • • • • • • 76

A. '.Iheory • • • • • • • • • • • • • • • • 76

B. Teohnologioal applications • • • • • • • • 78

III. Texture Development • • • • • • • • • • • 83

A. '.Iheoretioal study • • • • • • • • • • • • 83

B. Teohnologl.oal applioati.ons • • • • • • ' • • 100

IV. Possible Camneroial Production Methods • • • • • • 102

A. Caramelization in the packaging container • • • • 102

B• Carameliza ti cm before packaging • • • • • • • 107

c. Possible oamneroial product types • • • • • • • 111

v. Studies en the Changes O:Jourring During Storage ot

Caramelized Sweetened Ccmdensed Mille. • ~ ~ • • • • 112

VI. Summary. • • • • • • • • • • • • -· • • • • 122

SECTION V. STUDIES W mE DEVELOPMENT OF A POROUS WAFER FROll

I.

II.

III.

IV.

MIIK SOLIDS

Introduction

• • • • • • • • • • • • • • •

• • • • • • •

~eoretical Background Discussion

A. Bubble mechanics • • • •

B. Foam preparati an • • • •

•

•

•

•

• • • • • •

• • • • • •

• • • • • •

• • • • • •

Studies an Methods of, and Factors Affecting Aeration ot

lfilk Solids Solutions • • • • • • • • •

A. Methods of aeration • • • • • • • •

1. Whipping and/or injection o£ gas (air)

2. Cb.emical leavening • • • • •

3. ~ennal liberation of moisture vapour

4. Vacuum expansion •

B. Factors a.f'fecting aeration

•

•

•

•

• •

• •

•

•

•

• •

• •

• •

• •

• •

• •

•

•

•

•

•

•

•

•

•

•

•

1 • Introduction and literature review • • • •

2. Experimental ~tudies

3. Conclusions • • •

Method of Drying to a Solid Foam

A. Oven or hot air drying •

B. Vacuum foam drying • •

•

•

•

•

• • •

• • •

• •

• • •

• • •

• ' ' • •

' • • • •

• • • •

• • • • •

• • • • •

PAGE

• 125

• 126

• 127

• 127

• 131

• 132

• 132

• 132

• 132

• 135

• 135

• 137

• 137

• 141

• 159

• 161

• 161

• 167

v. Possible Camneroial Aspeots of this Wafer Type ot Product • 176

A. Texture • • • • • • • • • • • ! • ! • • 1 76

B. Flavour • • • • • • •

o. Use of f'ull cream milk solids

D. Packaging and storage • • •

• •

• •

• •

• • •

•

• • •

• •

•

•

' 177

. 1n • 178

TI • Stumnal'y • • • • • • • • • • • • • • • • • • 180

PAGE

SECTION VI. S1UDIES ON 'lHE DEVEWBIENT OF A CONC:ElimATED CARAMEL

FLAVOUR BASE • • • • • • • • • • • • • • • 182

I. Introduction • • • • • • • • • • • • • 183

II. Liquid Concentrate • • • • • • • • • • • • • • 183

III. Powiered Caramel Flavour • • • • • • • • • • • • 185

SECTION VII. SUGGESTICNS FOR FURmER STUDY • • • • • • • • • • 190

• • • • • • • • • • • • • • • • • • • • • • 195

BIBLIOGRAEHY • • • • • • • • • • • • • • • • • • • • 203

One readily demonstratable effect resulting fran the prolonged heat

treatment of milk is browning. A form of non-enzymic browning due to inter-

action of aldoses with free amino-groups occurs in many foods, and hence this

reaction is of broad significance in the food field; e.g., dry milk products (29),

processed potatoes (95), dried fruit (-l 02), dried whole eggs ( 73), dried meat (99),

and. liquid and. concentrated milk products (33,83). fue significance of browning

in food technology has two aspects - the desirable and the undesirable.

In many areas of the world today people are undernourished, malnourished,

and. even starved. At the same time in other parts of the world, food is abundant

to the point of substantial excess. Although many factors contribute to this

unbalance, food spoilage is an important considers.ti.en. Sane emess food oan

be processed and. stored in a practical manner involving little or no deter­

ioration, but sane of it faces spoilage despite man's preventive efforts. One

vexing problem of food spoilage is browning 'Whi~h may atteot many food. products.

1hese include dried food such as milk, eggs, f'rui ts, fruit juices, meat, fish

and vegetables ( 12) ; canned milk, fruit, and vegetables; and. other foods such

as molasses. Loss of palatability and nutri ti.ve value as well as undesirable

ohanges in physical properties frequently attend the brOWling of f'ood. to va.ry.i.ng

degrees of' intensity, depending an the stage to llhich the reaction has progressed.

~s is the undesirable aspeot of br01llling.

On the other hand, the Maillard reaction can make a positive cantributicn

to food. technology by producing desirable colours, flavours and arcmas in ~

foods auoh as re~to-serve oereal.s, toffees, roasted coffee, malted barley,

and baked goods (65). ibasting, bald.ng, roasting, and frying are processes

aimed at intentionally browning the f'ood.. Although there is acme loss of amino

acids llhen these flavours are produced, the loss is not usually of much import-

8ll0e and is accepted as a price 1'0rth paying. 'lhe Maillard. reaction can be

explai ted for particular purposes by the ad.di ti on of reduoing agents to the

food. For example, the inclusion of milk powder in a loaf of bread peDrl. ts

more even toasting at a lower temperature because of the presenoe of lactose.

Another example is the production of chiaken and meat-like flavours by heating

amino acids w1. th pentose sugars and. aldehydes. 'lhe distinotive caramel and

buttersootoh flavours derived frc:m dairy produots result from the bro"WDing of

milk or milk cc:mponents. 'Illus, i t is clear that bro..Ung has two aspects, both

of "filioh canoern the acceptability of man• s food.

It is the latter aspect ooh is of principal interest in the present

work. By prc:moting browning i n milk solids to varying degrees of intensity, a

range of palatable caramel flavours may be obtained. It is clear that dairy­

caramel flavours are appetizing by the fact that caramelized milk products are

very popular, and are eaten extensively in South America, India, and Europe.

Tradi ti anal products produced d.onestioally include 'Dulce de leohe' (Argentina,

Uruguay), 1Manyar blanco' (Cbile), and 1Khoa 1 (India). In Argentina, 2,800 tons

of 'DuJ.oe de leohe' are camnercially produced per annum; 98% of this produa:tian

is consumed intenial iy. Clearly then, many people enjoy d.airy~aramel flavours

"lilen purposely produced. With the realization that a potential market is

already present, the purpose of this thesis is to explore the possibility of

diversifying New Zeal.and. dairy produots by the prcmoted oaramelisatian of

milk solids.

A review of previous research into the browning reaotiai in milk showed

that muoh 'WOrk has been done and copious literature exists, but most of this

neglects the beneficial effects of nai-enzymio browning in millt and oanoentrates

on the deteriorative effects. Consequently, methods of measuring bl'O'ming

mainly involve measurements of the reactants and early intemediates as a basis

for inhibiting the early stages of browning. As a result· of this bias in

previous research, the first task of this study was to develop a method of

measuring pranoted browning ("caramelization") in milk. '.!he method finally

chosen was the reflectance measurement of colour.

A reliable method of measuring pranoted browning made possible a study

of the factors affecting pranoted browning, and caramel f'lavour development,

in S11eetened condensed milk. fue study was restricted to br01ll'li.ng in "liquid"

systems as the factors affecting browning in "dry" milk powder have been well

documented (65,83 ). In this context, there were t\'IO principal areas of interest

with regard to browning and associated changes in milk systems. One is practical

and conoerns the manipulation of prooess and produot variables suoh as tempera­

ture, time, pH, and moisture content, to obtain a controlled amount of browning.

'.!he other is f'und.amental and concerns me.king the knowledge of milk and its

behaviour as canplete as possible.

Without incorporation into palatable food structures and textures any

flavour is of little value as food. Henoe, the remainder of this thesis is an

exploration of the possibilities ot incorporating dairy caramel flavours into

conventional food textures, struotures, and types ?ihich are of proven palat­

ability. A survey of present food tonns marketed, . and a consideration of recent

trends in food marketing suggests that the following product types are of proven

consumer acceptance and worthy ot further study and development.

1. Sweet caramelized spread for use in the same way as

jams; i.e., spread, pie filling, cakes, etc.

2. Porous waf'er or bisoui t type of product - pe:rilapa for

use as a high protein supplement in a form llh:i.ch the

consumer is familiar with.

3. Concentrated dairy caramel flavour in pawder or liquid concentrate

foxm for general food flavouring.

4. Oanfeotions - sweets, toffees, milk caramel, hokey-pokey, etc.

( fue production of caramel confections is '91811 documented and

was not studied further.)

With an aim of developing these general produot types a :f'undamental study 118.S

undertaken to define the factors affecting flavour, colour, and texture of

browned milk solids.