Biopolymers Casein Its Preparation And Use A Practical Handbook

Biopolymers - Casein – Its Preparation And Use – A Practical Handbook

by

Robert Murray-Smith

Copyright 2014 Robert Murray-Smith

Smashwords Edition

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Contents

Preface

Introduction

Chapter I - Casein: Its Origin, Preparation And Properties.

Chapter II - Various Methods Of Preparing Casein.

Chapter III - Composition And Properties Of Casein.

Chapter IV - Casein Paints

Chapter V - Casein Adhesives And Putties.

Chapter VI - The Preparation Of Plastic Masses From Casein.

Chapter VII - Uses Of Casein In The Textile Industry, For Finishing

Colour Printing, Etc.

Chapter VIII - Sundry Applications Of Casein.

Chapter IX - Casein Compounds.

Appendixes

Appendix 1 - Resins

Appendix 2 - Balsams

Appendix 3 – Limes

Appendix 4 - Trituration

Appendix 5 - Caoutchouc

Appendix 6 - Glue.

Preface

The major use of casein currently is as a foodstuff. There have been some inroads recently to using it as a renewable biopolymer resource but development is pretty much in its infancy. This has been the case from the first extraction of casein as cheese to a brief period at the turn of the twentieth century when it enjoyed popularity as a plastic material - Galalith. That is until the outbreak of the Second World War where it disappeared into obscurity when faced with the demand for food production and later competition from petrochemical derived materials.

Casein belongs to that class of materials known as the albuminoids, a class of simple proteins such as keratin, gelatin, casein or collagen, that are insoluble in all neutral solvents and are currently enjoying a resurgence of interest as a result of the search for alternatives to the dwindling resource that are petrochemical derived plastics.

It is therefore easy to understand that our knowledge of this important material is somewhat imperfect, especially as regards its many applications: Literature on the subject in the academic press is still relatively rare, and general information on how to prepare and use this material is even rarer. It consequently seemed desirable to the author to prepare a work dealing with this material in an accessible form so that the home experimenter could approach this subject with a host of methods, tools and ideas in order to enable them to utilize the material in light of modern research and experimentation.

The bulk of the material is derived from texts that were prominent in the early part of the twentieth century as this is when most of the work regarding this material was done.

The first part treats of the preparation of casein from milk, which is done in all cases by the precipitation of the suspended casein compound from the milk with the aid of acids or a ferment (rennet), and its purification and drying. Following this, will be described the application of the casein paints and painting, the production of putties, plastic masses, etc., and finally some of its alternative uses for furthur consideration.

As most of this work was done in the early part of the century this volume represents little more than a rewrite and update of Sherrer’s text on the subject – no apology is made for this as the information is invaluable and should be made accessible to the modern audience.

Finally, it should be noted that the recipes presented in this book don’t represent end products in themselves but rather points of departure for further experimentation.

INTRODUCTION

Although casein, in the form of cheese, has played an important part in the diet of the human race, and has been produced in very large quantities for large part of human history, its technical utilisation has been almost entirely neglected except for a brief flirtation with it as a plastic material at the turn of the twentieth century. Its properties of dissolving in alkaline liquids and forming, in this condition, a good mucilage (which is a thick, gluey substance produced by nearly all plants and some microorganisms. A mucilage is a polar glycoprotein and an exopolysaccharide. Mucilage in plants plays a role in the storage of water and food, seed germination, and thickening membranes and is frequently used as glues) have long been known; but this was all, and it was only within a forty year period from the 1900s to around 1940 that any extensive technical application of casein occurred. However, leading up to and post the Second World War use and exploration of casein as a technically useful material almost ground completely to a halt. The main reasons for its demise as a material of interest revolved around the emergence of petrochemicals and the banning of its use for anything other than a foodstuff as a direct result of the war effort. However, with the recognition that petrochemicals are not an infinite resource and concerns with the environment coupled with huge over production of casein raw materials, milk, the situation has somewhat reversed and interest in casein as a renewable resource and a source of valuable plastic materials has once again arisen. This is a relatively new development and technical literature is somewhat spares and literature on how to create, use and form the material in a practical sense almost non-existant

In its history Casein has been used as paint, as a dressing for textiles, a cement and mucilage, in the production of plastic masses, for sizing paper, and various other purposes. In 1893, French chemist Auguste Trillat discovered the means to insolubilize casein by immersion in formaldehyde. Its original application as a foodstuff has not been lost sight of; its high nutritive value and its assimilability have led to the preparation of a number of artificial foods that are now extensively consumed particularly within the health food and body building market.

Post the demise of casein America and Germany attached considerable importance to the manufacture and treatment of casein. The Casein Company of America enjoyed a monopoly of the manufacture and sale of casein and its products in the United States. The Union Casein Company bought contracts with large dairies for several years ahead and The Casein Company of America took out a large number of patents, covering nearly the whole ground, from the precipitation of the casein from milk to the production of mechanical mixtures of casein, and utilized these patents as a means of bringing pressure to bear on small dairies and tie up the supply and production of casein and its products. Clearly all concerned saw the material as extremely important.

Casein formed an important article of commerce in America, especially in papermaking, the manufacture of sized papers, etc;

Perhaps the most famous use for casein based materials was in the formation of galalith

Galalith (Erinoid in the United Kingdom) is a synthetic plastic material manufactured by the interaction of casein and formaldehyde. Given a commercial name derived from the Greek words gala (milk) and lithos (stone), it is odourless, insoluble in water, biodegradable, antiallergenic, antistatic and virtually nonflammable.

Although it could not be molded once set, and was hence produced in sheets, it was inexpensive to produce due to its simple manufacture. Galalith could be cut, drilled, embossed and dyed without difficulty, and its structure manipulated to create a series of effects. No other plastic at the time could compete on price, and with ivory, horn and bone products becoming far more expensive; it found a natural home in the fashion industry.

This new plastic was presented at Paris Universal Exhibition in 1900. In France, Galalith was distributed by the Compagnie Française de Galalithe located near Paris in Levallois-Perret. As a result, the Jura area became the first one to use the material.

Marketed in the form of boards, pipes and rods, in 1913 thirty million litres (eight million US gallons) of milk were used to produce Galalith in Germany alone. In 1914, Syrolit Ltd gained the license for manufacture in the United Kingdom. Renaming itself Erinoid Ltd, it started manufacture in the Lightpill former woollen mill in Dudbridge, Stroud, Gloucestershire.

Galalith could produce gemstone imitations that looked strikingly real. In 1926 Gabrielle Coco Chanel published a picture of a short, simple black dress in Vogue. It was calf-length, straight, and decorated only by a few diagonal lines. Vogue called it Chanel’s Ford, as like the Model T, the little black dress was simple and accessible for women of all social classes. To accessorize the little black dress, Chanel revamped her designs, thus facilitating the breakthrough and mass popularity of costume jewelry. Artists such as Jacob Bengel and Auguste Bonaz, as well as for hair combs and accessories, used Galalith for striking Art Deco jewelry designs. By the 1930s, Galalith was also used for pens, umbrella handles, white piano keys (replacing natural ivory), and electrical goods, with world production at that time reaching 10,000 tons.

Although Galalith was historically cheap, the fact it could not be molded was a serious drawback which helped lead to its demise by commercial end users. Production slowed as the restrictions of World War II took effect and was furthur reduced due to new oil-derived wartime plastic developments. Production continued in Brazil until the 1960s when it finally ceased.

The main uses of casein today are as:

Paints

Casein paint is a fast-drying, water-soluble medium used by artists. Casein paint has been used since ancient Egyptian times as a form of tempera paint, and was widely used by commercial illustrators as the material of choice until the late 1960s when, with the advent of acrylic paint, casein became less popular. It is still widely used by scene painters, although acrylic has made inroads in that field as well.

Glue

Casein-based glues were popular for woodworking, including for aircraft, as late as the de Havilland Albatross airliner of 1936. Casein glue is also used in transformer manufacturing (specifically transformer board) due to its oil permeability. While largely replaced by synthetic resins, casein-based glues still have a use in certain niche applications, such as laminating fireproof doors and the labeling of bottles.

Cheese Making

Cheese consists of proteins and fat from milk, usually the milk of cows, buffalo, goats, or sheep. It is produced by coagulation of casein. Typically, the milk is acidified and then coagulated by the addition of rennet, containing a proteolytic enzyme, typically obtained from the stomachs of calves. The solids are separated and pressed into final form.

Unlike many proteins, casein is not coagulated by heat. During the process of clotting, milk-clotting proteases act on the soluble portion of the caseins, κ-casein, thus originating an unstable micellar state that results in clot formation. When coagulated with chymosin, casein is sometimes called paracasein. Chymosin (EC 3.4.23.4) is an aspartic protease that specifically hydrolyzes the peptide bond in Phe105-Met106 of κ-casein, and is considered to be the most efficient protease for the cheese-making industry (Rao et al., 1998). British terminology, on the other hand, uses the term caseinogen for the uncoagulated protein and casein for the coagulated protein. As it exists in milk, it is a salt of calcium.

Plastics and fiber/fibre

Some of the earliest plastics were based on casein. In particular, galalith was well known for use in buttons. Fiber can be made from extruded casein. Lanital, a fabric made from casein fiber (known as Aralac in the United States), was particularly popular in Italy during the