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Tanning Chemistry: The Science of Leather
Oleh Anthony D Covington dan William R Wise
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Mulai MembacaPanjangnya: 1,404 halaman12 jam
- Penerbit:
- Royal Society of Chemistry
- Dirilis:
- Nov 7, 2019
- ISBN:
- 9781788019071
- Format:
- Buku
Deskripsi
This book offers a state-of-the-art view of leather making, based on the scientific principles underpinning the technology. In particular, it contributes to the understanding of the modern leather industry, allowing practitioners to make judgements about day-to-day problems in the tannery and how change can be applied in a predictable way. Major themes running through the book are the economics and environmental impact of leather making and how these will ensure the sustainability of the industry.
This second edition of Tony Covington’s Tanning Chemistry is a revision, update and extension in collaboration with a new co-author, Will Wise. The update reflects the advances made in the past decade, including a discussion of the impact of new information concerning the chemistry of sulfide. The original chapters have been re-organised and new chapters on novel modes of reagent delivery and the principles of finishing are now included. Enzymology is addressed as a separate topic, as are environmental impact and the future of leather.
The book will be useful to all those involved in the supply chain, from farm, through students, chemical suppliers and tanners, to leather goods brands. Leather science is the key to understanding leather technology, to make it work, to make it work better and to keep it ahead of the competition.
Tindakan Buku
Mulai MembacaInformasi Buku
Tanning Chemistry: The Science of Leather
Oleh Anthony D Covington dan William R Wise
Panjangnya: 1,404 halaman12 jam
Deskripsi
This book offers a state-of-the-art view of leather making, based on the scientific principles underpinning the technology. In particular, it contributes to the understanding of the modern leather industry, allowing practitioners to make judgements about day-to-day problems in the tannery and how change can be applied in a predictable way. Major themes running through the book are the economics and environmental impact of leather making and how these will ensure the sustainability of the industry.
This second edition of Tony Covington’s Tanning Chemistry is a revision, update and extension in collaboration with a new co-author, Will Wise. The update reflects the advances made in the past decade, including a discussion of the impact of new information concerning the chemistry of sulfide. The original chapters have been re-organised and new chapters on novel modes of reagent delivery and the principles of finishing are now included. Enzymology is addressed as a separate topic, as are environmental impact and the future of leather.
The book will be useful to all those involved in the supply chain, from farm, through students, chemical suppliers and tanners, to leather goods brands. Leather science is the key to understanding leather technology, to make it work, to make it work better and to keep it ahead of the competition.
- Penerbit:
- Royal Society of Chemistry
- Dirilis:
- Nov 7, 2019
- ISBN:
- 9781788019071
- Format:
- Buku
Tentang penulis
Terkait dengan Tanning Chemistry
Pratinjau Buku
Tanning Chemistry - Anthony D Covington
Tanning Chemistry
The Science of Leather
2nd edition
Tanning Chemistry
The Science of Leather
2nd edition
By
Anthony D. Covington
The University of Northampton, UK
Email: tony.covington@northampton.ac.uk
and
William R. Wise
The University of Northampton, UK
Email: will.wise@northampton.ac.uk
Print ISBN: 978-1-78801-204-1
EPUB ISBN: 978-1-78801-907-1
A catalogue record for this book is available from the British Library
© Anthony D. Covington and William R. Wise 2020
All rights reserved
Apart from fair dealing for the purposes of research for non-commercial purposes or for private study, criticism or review, as permitted under the Copyright, Designs and Patents Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry or the copyright owner, or in the case of reproduction in accordance with the terms of licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page.
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Preface to the First Edition
Even in the 21st Century, the manufacture of leather retains an air of the dark arts, still somewhat shrouded in the mysteries of a millennia old, craft based industry. Despite the best efforts of a few scientists over the last century or so, much of the understanding of the principles of tanning is still based on received wisdom and experience. It has been my mission to contribute to changing the thinking in the industry, to continue building a body of scientific understanding, aimed at enhancing the sustainability of an industry which produces a unique group of materials, derived from a natural source.
This book is the culmination of a 40 year career in chemistry and the leather industry. My love of chemistry was fuelled at Ackworth School, Pontefract, UK, by Phillips Harris, a genius of a teacher. I obtained an HNC in chemistry at Newcastle Polytechnic (now the University of Northumbria), followed by the Graduateship of the Royal Institute of Chemistry (now the Royal Society of Chemistry) at Teesside Polytechnic (now the University of Teesside). This provided me with a firm basis in general chemistry, with a strong emphasis on practical skills – mine was the last year the GRIC involved four days of practicals as part of finals! My chemistry experience was enhanced in my doctoral studies in physical organic chemistry at Stirling University under the invaluable supervision of Professor R. P. Bell FRS, followed by post doctoral research in physical chemistry with Professor Arthur Covington DSc (coincidence, no relation) at the University of Newcastle upon Tyne – the city of my birth.
In 1976 I joined the British Leather Manufacturers' Association (later to become BLC The Leather Technology Centre of Northampton, UK), where I spent 18 years engaged in research and development, industrial consultancy and problem solving, mostly under Director Dr Robert Sykes OBE. The value of this period was in my exposure to a wide range of aspects of the global leather industry, particularly the opportunity to work in different types of tanneries around the world. At this time, I was initiated into doctoral supervision, in collaboration with Dr Richard Hancock of the Royal Holloway campus of the University of London: the student was Ioannis Ioannidis, later to become a leading light in major European projects.
In 1995 I was appointed by Nene College, later to be The University of Northampton, to teach leather science in the British School of Leather Technology. It is this latter period that proved to be the most fruitful in the development of my understanding of the subject, stimulated in the main by the questioning of my students. It has been said that to understand a subject fundamentally, one should try teaching it: I can vouch for the truth of that observation. Only when I was confronted with classes of (mostly overseas) students, to whom I was trying to convey a logical approach to thinking about the subject, did I become aware of the inconsistencies and inaccuracies of received wisdom, but with which I had worked without critical review for two decades. Since few scientists in the last quarter of a century have been working on the principles of leather making, these problems in the body of knowledge had to be addressed by my research group.
Contrary to the belief expressed in some factions in higher education, leather technology and leather science are real subjects: they are full of technical and scientific rigour and difficulty, typically at the overlapping regions between conventional disciplines, because they are interdisciplinary subjects. Leather technology is fully deserving of recognition and respect in the field of the applied sciences. Those who beg to differ are challenged to examine the courses and examinations my students must face; dealing as they do with chemistry, biochemistry, biology, physics and materials science, not to mention management and legislation, and where additionally the topics are embedded with new concepts from emerging research.
In science and technology, we all stand on the shoulders of giants. I have been privileged to meet, befriend and work with the best. There are too many to mention them all, but here are a few, in no particular order of precedence: Eckhart Heidemann, Betty Haines, Gunther Reich, Bi Shi, David Bailey, Steve Feairheller, Richard Daniels, Jaume Cot, Roy Thomson, Alberto Sofia, Sjef Langerwerf, Gabi Renner and Jakov Buljan. I must also include my old friend Shri Dr T. Ramasami, former Director of the Central Leather Research Institute, Chennai, India, to whom I am related – not by blood, but by academic ties – his PhD supervisor was a PhD student of my PhD supervisor.
For any academic, his or her relationship with their postgraduate students creates an unusual bond, quite unlike any other relationship. I have been fortunate in having had many highly gifted students, whose contribution to my thinking and understanding has been immense. Nor do I forget the contributions of my colleagues, both at BLC and in the British School of Leather Technology.
As I reflect on a lifetime in science, my only regret is that the future of leather science as a subject is uncertain. There are very few of us leather scientists around. Moreover, such is the current disinclination towards financing science, especially applied science, more especially fundamental applied science, whether in industry or in higher education, it seems unlikely that leather science will command the attention of many future practitioners in the field. Nevertheless, there will always be a need in the global industry for highly qualified practitioner leather technologists and it is to them that I direct this text.
My undergraduate students have often distinguished a clear demarcation between leather technology and leather science, on the basis that leather technology is the easier option, because it is mostly concerned with the practicalities of making leather; but leather science is perceived as more difficult, perhaps just because it is called science. I have always shared Pasteur's view that there is no real boundary between science and technology and especially leather technology and leather science; the former is merely the application of the latter, they are but two sides of the same coin. Indeed, my personal view is that leather science is easier, because it is entirely logical. But then I would say that, wouldn't I?
Tony Covington
Preface to the Second Edition
Sir William Thompson, aka Baron Kelvin of Largs, recognised and respected in his day for his contributions to physics at a global level, was once famously quoted in 1900 as saying ‘There is nothing new to be discovered in physics now. All that remains is more and more precise measurement’. This bold statement has been recognised as laughably inaccurate, with countless physicists, including Einstein, proving that there will always be questions that need to be answered, fundamentals that need to be understood and improvements that need to be made beyond simply improving precision of measurement.
Because we have been making leather for over 5000 years, the outside world is similar in that it perceives the leather industry – and the science that underpins it – to be stagnant, with nothing new to discover. However, those within the industry know that nothing could be further from the truth!
As was stated in the First Edition of this book, much of what we do today remains more of an ‘art’ than a science. I have every intention of following in the footsteps of my predecessors and mentors in ensuring that we continue to gain a better scientific understanding of what has been practiced over centuries. I am firmly of the belief that from an increase in the understanding of the science we will progress the industry towards an increasingly sustainable future – from subtle changes that make gains in process efficiency through to exploring the paradigm shifts that move us entirely away from ‘the norms’ that we know today.
Despite the desire to follow in the footsteps of some great scientists who have moved the area of leather science on enormously in the last half century, I have not always been involved with the leather industry; my background and higher education are in chemistry. My interests in ‘science’ started at an early age – encouraged by both my mother and father – and quickly developed into a passion. I went to university to read a BSc in chemistry, swiftly followed by an MSc in green chemistry and a PhD in organic chemistry. In 2014, after three years conducting postdoctoral research on developing sustainable alternatives to traditional polyolefin-based polymers, I took up my current post as a Senior Lecturer within the Institute for Creative Leather Technologies (ICLT) at the University of Northampton.
Prior to my appointment in 2014 and as ‘an outsider’ to the leather industry, I knew very little about the industry; I certainly would not have considered the amount of applied interdisciplinary science that it relied upon to make a material I took for granted. People often snigger when I explain what I now do as a job, but much of this stems from a lack of understanding – only when the scope of the science is explained do they begin to comprehend quite how complex the area is. I am now desperate to encourage more people to pursue leather manufacture/research as a career, to take leather science seriously and to give it the recognition it deserves. For me, this book acts as the starting point …
Will Wise
Dedication
I dedicate this Second Edition to my wife Rebecca and my three daughters Emily, Ella and Sophie, because without their support I would not have been able to achieve so much in such a short space of time. They do not question where I am or what I'm doing, they just ensure that I know I'm loved and supported in every endeavour. I should also dedicate this book to my mother and father; it was because of them that I originally became interested in science and have the unquenchable thirst to understand why and how things work that now drives my research. My brother also deserves a dedication – those with siblings will understand the competitive drive that develops as a result of ‘sibling rivalry’ and the subsequent need to achieve the best that you are capable of in everything that you do. Finally, I dedicate this book to the friends and family, of whom there are too many to single out, that have supported me throughout my life, helped me when I needed it and remained a constant source of encouragement.
My thanks to you all.
Will Wise
Acknowledgements
Rachel Garwood MSc, inspirational Director of the Institute for Creative Leather Technologies, The University of Northampton.
Our late beloved colleague, Amanda Michel.
The support of Professor Nick Petford DSc, Vice Chancellor of the University of Northampton.
The support of the Masters and Court of the Worshipful Company of Leathersellers of the City of London.
Contents
Introduction
Introduction to the Second Edition
Glossary of Termss
1 Collagen and Skin Structure 1
1.1 Introduction
1.2 The Hierarchy of Collagen Structure
1.2.1 Primary Structure
1.2.2 Secondary Structure
1.2.3 Tertiary Structure
1.2.4 Quaternary Structure
1.3 The Triple Helix
1.4 Isoelectric Point
1.5 Collagen and Water
1.6 The Quarter Stagger Array
1.7 Fibrils
1.8 Fibril Bundles
1.9 Fibres
1.10 Other Collagens
1.10.1 Type III Collagen
1.10.2 Type IV Collagen
1.10.3 Type VII Collagen
1.11 The Chemistry of Collagen
1.12 Hydrothermal Stability
References
2 Skin and Its Components 32
2.1 Introduction
2.1.1 Epidermis
2.1.2 Grain
2.1.3 Junction
2.1.4 Corium
2.1.5 The Flesh Layer
2.1.6 Flesh
2.2 Skin Features and Components
2.2.1 Hair or Wool
2.2.2 Follicles
2.2.3 Erector Pili Muscle
2.2.4 Sweat Glands
2.2.5 Veins and Arteries
2.2.6 Elastin
2.3 Non-structural Components of Skin
2.3.1 Glycosaminoglycans (GAGs)
2.3.2 Melanins
2.4 The Skin
2.4.1 Area of Skin or Leather
2.5 Processing
2.5.1 Splitting
2.5.2 Grain-to-corium Thickness Ratio
2.5.3 Fleshing
2.5.4 Dung
2.6 Variations in Skin Structure Due to Species
2.6.1 Hereford Cattle and Vertical Fibre
2.6.2 Sheepskin
2.6.3 Cutaneous Fat
References
3 Curing and Preservation of Hides and Skins 81
3.1 Introduction
3.2 Drying
3.3 Salting
3.3.1 Stacking
3.3.2 Drum Curing
3.3.3 Types of Salt
3.3.4 Additives for Salt
3.3.5 Dry Salting
3.3.6 Brining
3.4 Alternative Osmolytes
3.4.1 Potassium Chloride
3.4.2 Sugars
3.4.3 Sodium Silicate
3.4.4 Poly(Ethylene Glycol)
3.5 pH Control
3.6 Temperature Control
3.6.1 Chilling
3.6.2 Iceing
3.6.3 Biocide Ice
3.6.4 Freezing
3.7 Biocides
3.8 Radiation Curing
3.9 Fresh Stock
References
4 Soaking 108
4.1 Introduction to Beamhouse Processing
4.2 The Soaking Process
4.2.1 Rehydration
4.2.2 Removal of Salt
4.2.3 Cleaning the Pelt
4.2.4 Removal of Non-structural Proteins
4.2.5 Removal of Dung
4.2.6 Removal of Hyaluronic Acid
4.3 Conditions in Soaking
4.3.1 Long Float
4.3.2 Change of Float
4.3.3 Temperature
4.3.4 pH
4.3.5 Time
4.3.6 Mechanical Action
4.4 Components of Soaking Solutions
4.4.1 Water
4.4.2 Detergents
4.4.3 Soaking Enzymes
4.5 Biocides
4.5.1 pH
4.5.2 Temperature
4.5.3 Time
4.5.4 Fresh Hides or Skins
4.5.5 Dried Hides
4.5.6 Dirty Rawstock
4.5.7 Putrefied Rawstock
4.5.8 Nature of the Cure
4.5.9 Water Quality
4.5.10 Use of Enzymes
4.5.11 Soaking Procedure
4.6 Role of the Erector Pili Muscle
References
5 Unhairing 130
5.1 Introduction
5.2 Keratin and the Structure of Hair
5.3 Hair Burning
5.3.1 The Role of Swelling
5.3.2 Chemical Variations
5.4 Immunisation
5.5 Hair Saving
5.6 Variations in Unhairing Technologies
5.6.1 Heidemann’s Darmstadt Process
5.6.2 Oxidative Unhairing
5.6.3 Reductive Unhairing
5.6.4 Acid Unhairing
5.7 Enzymes in Unhairing
5.7.1 Enzyme-assisted Chemical Unhairing
5.7.2 Chemical-assisted Enzyme Unhairing
5.7.3 Enzyme Hair Saving
5.7.4 Keratinase
5.8 Painting
5.9 The Role of Shaving in Unhairing
References
6 Liming 157
6.1 Introduction
6.1.1 Float
6.1.2 pH
6.1.3 Temperature
6.1.4 Time
6.2 Purposes of Liming
6.2.1 Removal of the Non-collagenous Components of the Skin
6.2.2 Splitting the Fibre Structure at the Level of the Fibril Bundles
6.2.3 Swelling the Pelt
6.2.4 Hydrolysis of Peptide Bonds
6.2.5 Hydrolysis of Amide Sidechains
6.2.6 Hydrolysis of Guanidino Sidechains
6.2.7 Removal of Dermatan Sulfate
6.2.8 Fat Hydrolysis
6.3 Variations in Liming
6.3.1 Chemical Variations
6.3.2 pH Variations
6.3.3 Biochemical Variations
6.3.4 Recycling
6.4 Limeblast
References
7 Deliming 181
7.1 Introduction
7.2 Deliming Agents
7.2.1 Water
7.2.2 Strong Acids
7.2.3 Weak Acids
7.2.4 Acidic Salts
7.2.5 Ammonium Salts
7.2.6 Alternative Buffers
7.2.7 Hydroxyl ‘Sinks’
7.2.8 Carbon Dioxide
7.3 Melanin
7.4 Limeblast
References
8 Bating 196
8.1 Introduction
8.2 Factors Affecting Enzyme Catalysis
8.2.1 Temperature
8.2.2 pH
8.2.3 Concentration: Bate Formulations
8.2.4 Time
8.2.5 Origin
8.3 Monitoring Bating
References
9 Pickling 204
9.1 Introduction
9.2 Processing Conditions
9.2.1 Float
9.2.2 Salt
9.3 Lyotropic Swelling
9.4 Sulfuric Acid
9.5 Hydrochloric Acid
9.6 Formic Acid
9.7 Colour
9.8 Non-swelling Acids
9.9 Pickle Formulations
9.10 Implications of Pickling for Chrome Tanning
9.11 No-pickle Processing
References
10 Tanning 224
10.1 Introduction
10.2 Hydrothermal Stability
10.2.1 Shrinkage Temperature (Ts)
10.2.2 Boil Test
10.2.3 Differential Scanning Calorimetry
10.2.4 Hydrothermal Isometric Tension
10.3 Historical Tannages
10.3.1 Sulfur Tanning
10.3.2 Silica Tanning
10.3.3 Phosphate Tanning
10.3.4 Quinone Tanning
10.3.5 Aldehydes
10.3.6 Furfuryl Alcohol
10.3.7 Sulfite Cellulose (Lignosulfonate)
References
11 Mineral Tanning: Chromium(iii) 243
11.1 Introduction
11.2 Preparation of Chrome Tanning Salts
11.3 Brief Review of the Development of Chrome Tanning
11.4 Chromium(III) Chemistry
11.5 Chrome Tanning Reaction
11.6 Basification
11.6.1 Soluble Alkaline Salts
11.6.2 Carboxylate Salts
11.6.3 Other Basic Salts
11.6.4 Self-basifying Salts
11.7 Avoiding Basification
11.8 Reactivity at High Basicity
11.9 Role of Temperature
11.10 Relative Effects of pH and Temperature
11.11 Masking
11.11.1 Polycarboxylates
11.11.2 Other Chemistries
11.12 Stability of Chrome-tanned Leather
11.13 Role of Sulfate in the Chrome Tanning Mechanism
11.14 Role of the Counterion in Chrome Tanning
11.15 Role of the Solvent
11.16 Role of Ethanolamine
11.17 Nature and State of the Substrate
11.17.1 Modifying the Substrate
11.18 Chromium(VI) and Leather
References
12 Mineral Tanning 308
12.1 Introduction
12.1.1 Blocks and Groups of the Periodic Table
12.2 Experimental Tanning Reviews
12.3 Aluminium in Leather Making
12.3.1 Alum Pickle
12.3.2 Suede
12.3.3 Furskins
12.3.4 Semi-alum Tannage
12.3.5 Aluminium Silicate
12.3.6 Mixed Complexes with Aluminium
12.3.7 Chrome Uptake
12.4 Titanium Tanning
12.5 Zirconium Tanning
12.6 Iron Tanning
12.7 Zinc(II)
12.8 Mixed Mineral Tannages
12.9 Overview
References
13 Vegetable Tanning 336
13.1 Introduction
13.2 Vegetable Tannin Classification
13.2.1 Hydrolysable Tannins
13.2.2 Condensed Tannins
13.2.3 Complex Tannins
13.3 General Properties of Vegetable Tannins
13.4 Practical Vegetable Tanning
13.5 Modern Vegetable Tanning
13.5.1 Countercurrent Pit Tanning
13.5.2 Rockers
13.5.3 Ultrasound
13.6 Other Vegetable Tanning Technologies
13.7 Combination Tanning
13.7.1 Semi-metal Tanning
13.7.2 General Properties of Semi-metal Leathers
13.7.3 Semi-chrome Tanning
13.8 Condensed Tannins and Aldehydic Crosslinkers
References
14 Other Tannages 375
14.1 Oil Tanning
14.2 Sulfonyl Chloride
14.3 Syntans
14.3.1 Auxiliary Syntans
14.3.2 Retans
14.3.3 Replacement Syntans
14.3.4 Other Syntans
14.4 Resins
14.5 Aldehydes and Aldehydic Tanning Agents
14.5.1 Introduction
14.5.2 Formaldehyde
14.5.3 Glutaraldehyde
14.5.4 Other Aliphatic Aldehydes
14.6 Aldehydic Tanning Agents
14.6.1 Oxazolidines
14.6.2 Phosphonium Salts
14.7 Other Tanning Applications
14.7.1 Wet White
14.8 Miscellaneous Tannages
14.8.1 Epoxide Tannage
14.8.2 Isocyanate Tannage
14.8.3 Aromatic Heterocycles
14.8.4 Multifunctional Reagents
References
15 Post-tanning 409
15.1 Definition
15.2 Relationship Between Tanning and Post-tanning
15.3 Chrome Retanning
15.4 Sequence of Post-tanning Steps
15.5 Principles of Post-tanning
15.5.1 Mechanisms of Post-tanning
15.5.2 Role of the Isoelectric Point
15.5.3 Role of the Peptide Link
15.5.4 Role of the Sulfonate Group
15.6 Coordinating Post-tanning Processes
15.6.1 Neutralise and Retan
15.6.2 Retan and Dye
15.6.3 Retan and Fatliquor
15.6.4 Dye and Fatliquor
15.6.5 Retan, Dye and Fatliquor
15.7 Dynamic Mechanical Thermal Analysis (DMTA)
References
16 Dyeing 434
16.1 Introduction
16.2 Acid Dyes
16.3 Basic Dyes
16.4 Direct Dyes
16.5 Mordant Dyes
16.6 Premetallised Dyes
16.6.1 1 : 1 Premetallised Dyes
16.6.2 1 : 2 Premetallised Dyes
16.7 Aryl Carbonium Dyes
16.8 Reactive Dyes
16.9 Sulfur Dyes
16.10 Fungal Dyes
16.11 Dye Reactivity and Fixation
16.12 Role of the Substrate
16.12.1 Chrome-tanned Leather
16.12.2 Vegetable-tanned Leather
16.12.3 Other Tannages
16.13 Dyeing Auxiliaries: Levelling and Penetrating Agents
16.13.1 Anionic Auxiliaries
16.13.2 Auxiliaries that Complex with Dyestuff
16.13.3 Auxiliaries that Have Affinity for Both Leather and Dye
16.13.4 Intensifying Agents
16.13.5 Cationic Tannages
16.13.6 Cationic Auxiliaries
16.14 Alternative Colouring Methods
References
17 Fatliquoring 462
17.1 Introduction
17.2 Anionic Fatliquors
17.2.1 Sulfated Fatliquors
17.2.2 Sulfited Fatliquors
17.3 Soap Fatliquors
17.4 Cationic Fatliquors
17.5 Non-ionic Fatliquors
17.5.1 Alkyl Ethylene Oxide Condensates
17.5.2 Protein Emulsifiers
17.6 Multi-charged Fatliquors
17.7 Amphoteric Fatliquors
17.8 Solvent Fatliquors
17.9 Complexing Fatliquors/Water Resistance Treatments
17.10 Silicone Fatliquors
17.11 ‘Solid’ Fatliquors
17.12 Water Resistance
17.12.1 Introduction
17.12.2 Principles of Conferring Water Resistance
17.12.3 Chemistries of Water Resistance Treatments
References
18 Enzymology 497
18.1 Introduction
18.2 Kinetics
18.3 Enzyme Structure
18.4 Mechanisms
18.4.1 Lock and Key
18.4.2 Induced Fit
18.4.3 Quantum Mechanical Tunnelling
18.4.4 Michaelis–Menten
18.5 Active Site
18.6 Factors Affecting Enzyme Catalysis
18.6.1 Temperature
18.6.2 pH
18.6.3 Inhibition
18.7 Enzyme Assays
18.7.1 Enzyme Assays for Bating Activity
18.8 Enzymology of Leather Making: Current, Potential and Future
18.8.1 Enzymes in Soaking
18.8.2 Enzymes in Unhairing
18.8.3 Enzymes in Liming
18.8.4 Enzymes in Deliming
18.8.5 Enzymes in Bating
18.8.6 Enzymes in Pickling
18.8.7 Enzymes in Degreasing
18.8.8 Enzymes in Wet Blue Production
18.8.9 Enzymes in Other Tanning Processes
18.8.10 Enzymes in Post-tanning Processes
18.8.11 Enzymes in the Treatment of Untanned Waste
18.8.12 Enzymes in the Treatment of Tanned Waste
18.8.13 Enzymes in Other Areas of Processing
References
19 Reagent Delivery 523
19.1 Introduction
19.2 Low Float
19.3 Zero-float Processing
19.4 Non-aqueous Floats
19.4.1 Introduction
19.4.2 Paraffin Processing
19.4.3 Organic Solvents
19.4.4 Supercritical Carbon Dioxide
19.4.5 Compressed Gases
19.4.6 Bead Processing
19.4.7 Ionic Liquids
19.4.8 Deep Eutectic Solvents
19.5 Direct Injection
19.6 Overview
References
20 Drying 538
20.1 Introduction
20.2 Viscoelastic Materials
20.3 Leather Drying Stages
20.4 Role of Temperature with Moisture
20.5 Drying in Phases
20.6 Leather as a Material
20.7 Overview
References
21 Finishing 554
21.1 Introduction
21.2 Polymers for Finishing
21.2.1 Urethane
21.2.2 Acrylic
21.2.3 Nitrocellulose
21.2.4 Protein
21.2.5 Other Components Including Dyes and Pigments
21.3 Adhesion
21.3.1 Drying of the Finish
21.3.2 Surface Wetting
21.3.3 Types of Adhesion
21.4 Overview
References
22 Environmental Impact 572
22.1 Introduction
22.2 Waste or Co-products
22.2.1 Solid Waste
22.2.2 Liquid Waste
22.2.3 Gaseous Waste
22.3 Overview
References
23 Theory of Tanning: the Concept of Link–Lock 583
23.1 Introduction
23.2 Discussion of the Evidence
23.3 Conclusion
References
24 The Future of Tanning Chemistry 598
24.1 Introduction: the Future of Chrome Tanning
24.2 Other Mineral Tanning Options
24.3 Non-chrome Tanning for ‘Chrome-free’ Leather
24.4 Single Tanning Options
24.5 Tanning Combinations
24.6 Leather Properties
24.7 Organic Tanning Options
24.7.1 Polyphenol Chemistry
24.7.2 Polymer and Crosslinker
24.8 Natural Tanning Agents
24.8.1 Carbohydrates
24.8.2 ‘Bog Body’ Chemistry
24.8.3 Henna
24.8.4 Nordihydroguaiaretic Acid (NDGA)
24.8.5 Genepin
24.8.6 Oleuropein
24.8.7 Other Iridoids
24.9 Other Reagents
24.10 Compact Tanning
24.11 Alternative Technologies
24.12 Overview
24.13 Conclusions
References
25 The Future for Leather 627
25.1 Introduction
25.2 Progressive Change
25.2.1 Development
25.2.2 Innovation
25.2.3 Revolution
25.3 Prediction
25.3.1 Processing Conditions
25.3.2 Beamhouse
25.3.3 Liming
25.3.4 Bating
25.3.5 Pickling
25.4 Tanning/Post-tanning
25.4.1 Multiple Reactions
25.4.2 Post-tanning
25.4.3 Influence of Charge
25.4.4 Finishing
25.5 Reverse Analysis
25.6 Overview
25.7 Conclusions
References
Subject Index
Introduction
This treatise is a discussion of the leather making process from the point of view of the scientific principles involved. The approach adopted here is to build an understanding of the steps involved, particularly the chemistry of tanning, by starting at the beginning of the industrial process and going on to the end. This means starting with an understanding of the nature, structure and properties of the material with which we make leather, then considering what to do with it, how to do it and what the outcomes of the transformations may be.
Leather is made from (usually) the hides and skins of animals – large animals such as cattle have hides, small animals such as sheep have skins. The skin of any animal is largely composed of the protein collagen, so it is the chemistry of this fibrous protein and the properties it confers to the skin with which the tanner is most concerned. In addition, other components of the skin impact on processing, impact on the chemistry of the material and impact on the properties of the product, leather. Therefore, it is useful to understand the relationships between skin structure at the molecular and macro levels, the changes imposed by modifying the chemistry of the material and the eventual properties of the leather. Consequently, these aspects of the subject will be addressed in the following order: collagen chemistry, collagen structure, skin structure, processing to prepare for tanning, the tanning processes and processing after tanning.
Leather making is a traditional industry, after all it has been in existence since time immemorial, certainly over 5000 years, because the industry was established at the time of the Hammurabi Code (1795–1750 BC), when Article 274 laid down the wages for tanners and curriers. ¹ Indeed, the use of animal skins is one of man's older technologies, perhaps only predated by tool making. In the modern world, the global leather industry exists because meat eating exists. Hence, most leather made around the world comes from cattle, sheep, pigs and goats. One of the byproducts of the meat industry is the hides and skins: considering that the annual kill of cattle alone is of the order of 300 million, such a byproduct, amounting to 10–20 million tonnes in weight, would pose a significant environmental impact if it were not used by tanners. Leather makers around the world perform the ultimate example of adding value: an unwanted, discarded byproduct from one industry is turned into one of the most desired and widely applied materials in the world. Unfortunately, one tonne of hide is converted into only 200 kg of leather: the difference is waste, pollutants or byproducts, depending on your point of view. So, the problems with which tanners must contend become apparent.
Here, notably, there is a difference between the leather industry and the fur industry. In general, tanners process the skins of animals killed for the consumption of their carcases: in the fur trade, the skin is the important part of the animal and the carcase may be the byproduct, albeit perhaps turned into fertiliser. The processes for preparing and stabilising furskins have similarities with tanning, but the chemistries can be significantly different. However, the industries have traditionally been separate. Within the leather trade, some skins are processed from animals sustainably farmed in part for their skins, e.g. ostrich and alligator. It is important to emphasise that any animals specified by CITES (Convention on International Trade in Endangered Species) are not part of the ethical global leather industry.
It might appear anachronistic that such an old established technology should still be relevant today, particularly because some of those traditional technologies for making specific leathers survive in the modern industry. However, it is worth considering the properties and performance of modern leathers, in comparison to other modern materials. The suitability of leather for shoe manufacture is based upon the twin abilities of being able to exclude water, but allow air and water vapour to pass through the cross section of the upper: this is the basis of foot comfort when shod. The properties are so important that attempts have been made to mimic them in synthetic materials, the so-called poromerics. To date, none has been successful: witness the failure of Corfam in the 1960s, documented by Kanigel. ² Similarly, the reconstituting of leather fibres into a polymer matrix creates materials that cannot exhibit all the properties of leather, it merely creates other versions of poromerics. Strictly, all such materials cannot carry names connoting leather, since the definition of leather is based on the requirement that it must be made from the intact hide or skin of an animal. ³
The properties of leather do not limit its use only as shoe upper material. The natural structure of leather, founded in the properties of the protein collagen with chemical modification, confers the unique ability to function within the temperature range at least −100 to +130 °C, unmatched by any other material: synthetic materials either soften at high temperature or become brittle at low temperature. However, the continuing popularity of leather is based on the way it feels, the way it looks, the way it interacts with and moulds to the body, the way it wears in use, even the way it smells (for information – ‘essence of leather’ is plant polyphenol extract plus a little fish oil). The aesthetics of leather ensure it is likely to remain the preferred material of choice for many modern applications: shoes, clothing, upholstery, belts, handbags, etc. Importantly, the choice is supported by its performance. For example, the high hydrothermal stability of modern chromium(III) tanned leather allows it to be used in rapid mass production processes, in which shoe uppers are moulded directly onto melted polymeric soles; other leathers can be used to make foundry workers' safety gaiters because they can resist splashing from molten metal streams, even liquid steel, clothing leathers can be steam pressed, etc. The best material for motorcyclists is leather, because, in the event of the rider coming off the bike, the frictional heat of the skidding action over the road surface will not cause the material of the clothing to melt and consequently it is not fused into the rider's soft tissues.
The properties of leather depend on the origin of the raw materials, how the pelt is prepared for chemical modification, how that modification is conferred chemically, how the leather is lubricated and finally how the surfaces are prepared. Leather can be made as stiff and as tough as wood, as soft and flexible as cloth and anything in between. It is the traditional art and craft of the leather technologist to control the parameters and variables of processing to make leathers with defined, desired or required properties. It is from the creativity of the leather scientist that the range of leathers that can be made is continually widening.
As a traditional craft, leather making has its own jargon, built up over centuries, but much of which has no clear origin. Some of the terms are set out in Glossary below and more can be found in the British Standard Glossary of Leather Terms. ³
Leather scientists and technologists do not restrict their attention to leather alone. Leather is merely one set of examples within a range of collagenic biomaterials; there are many more already used in industry and many more can be developed: that should become clear by reading this text. Any application of proteinaceous materials, particularly collagen, and especially where the protein is modified in some way, is exploiting a biomaterial. For example, fixing of organic specimens in histology for microscopy study is using tanning technology, as is the stabilisation of medical sutures, e.g. in chromic catgut, when the rate of dissolution in the body is controlled by the degree of modification of the tissue by chrome tanning, the techniques of increasing the ‘weight’ of silk use tanning chemistry and so on. Therefore, clearly, the transfer of scientific and technological principles from the leather industry into other sectors is practical, feasible, desirable and full of potential.
It will become apparent from this text that the leather field has borrowed from other areas of science, often just using the principles rather than following developments in these subjects. In the past, tanners exploited technology and biotechnology long before the science was completely understood: so no change there! Hence, it is clear that some aspects of the development of the technology of the leather industry and progress in that technology have been slow, indeed Thomson has argued that the industrial revolution in leather making took place one hundred years after it began to transform the rest of industry. ⁴ The slow rate of change was compounded by the inherent conservatism of tanners, aware that change in processes and procedures can be detrimental to leather quality and performance; hence avoidance of change was the lesser of the twin evils of lack of technical progress or risking loss of money.
The continuing importance of leather production in the world cannot be under estimated. As a labour intensive operation, it is especially applicable to the developing economies. Moreover, in those countries, the industry offers significant employment opportunities for women: it is recognised that giving women the power to control the economics of the family has a potent stabilising effect on society. It has been argued that that movement of the global industry to the east and to the south has taken place to exploit cheaper labour and less stringent environmental legislation. The former is certainly the case, although the cheaper labour is becoming noticeably less cheap. The latter is not true: consent limits for discharges to the environment are surprisingly consistent throughout the world; ⁵ nowhere is the legislation on pollution significantly lax, it is merely the enforcement that varies. The perception that the leather industry is a dirty polluter is largely out of date. However, this does not mean that it can be assumed to be generally clean – unfortunately, there is still a long way to go. It is an important function of leather science to provide the technologists with sufficient understanding of the principles of the chemistry and biochemistry of processing for them to be able to make improving changes in the operations. Table I.1 characterises this progression towards zeroenvironmental impact.
Table I.1 Progression towards zero environmental impact
Developments in this direction should ideally be economically attractive at the same time, including using waste streams, by adding value to the byproducts. Since we are dealing here with an applied, industrial science, the economics of the operation should never be far from the analytical mind. Making money is a big incentive for change.
The text of this book is designed to be scientific, to define as much as possible the principles underpinning the complex technology of leather making. Hence, it is part of the function of this text to point the way forward, to contribute to the sustainability of the global industry, always based on a fundamental understanding of those principles.
There are not applied sciences… there are only applications of the science and this is a very different matter. The study of the applications of science is very easy to anyone who is the master of the theory of it.
Louis Pasteur. ⁶
References
1. R.Reed, Ancient Skins, Parchments and Leathers, Seminar Press, 1972.
2. R.Kanigel, Faux Real, Joseph Henry Press, Washington DC, 2007.
3. British Standard Glossary of Leather Terms, British Standards Institution, BS 2780, 1983.
4. R. S. Thomson, Trans., Newcomen Soc., 1981, 53, 139.
5. J. Buljan and M. Bosnic, World Leather, 1994, 7(6), 54.
6. E. Haslam, J. Soc. Leather Technol. Chem., 1988, 72(2), 45.
Introduction to the Second Edition
This Second Edition builds on the First Edition, bringing the science of leather making up to date. It was noticeable that the pace of change was slow in the earlier phases of leather production (apart from the shock of sulfide), but more rapid in tanning and post-tanning, if the references are anything to go by. The content of the book reflects how the subject has changed in the last decade – and the introduction of a co-author.
The text has been expanded to place more emphasis on the biochemistry of processing, to address the subject of reagent delivery and to include the science of finishing. As before, environmental impact and sustainability are at the heart of leather science, as they must be when we consider the future of processing as we see it today.
Anthony D. Covington
William R. Wise
Glossary of Terms
1Collagen and Skin Structure
1.1 Introduction
At the heart of the leather-making process is the raw material, hides and skins. As the largest organ of the body of mammals, the skin is a complex structure, providing protection against the environment and affording temperature control, but it is also strong enough to retain, for example, the insides of a 1 tonne cow. Skin is primarily composed of the protein collagen and it is the inherent properties and potential for chemical modification of this protein that offer the tanner the opportunity to make a desirable product from an unappealing starting material. It is part of the tanner's job and skill to purify this starting material, allowing it to be converted into a product that is both desirable and useful in modern life.
Collagen is a generic name for a family of at least 28 distinct collagen types, each serving different functions in animals, importantly as connective tissues. ¹,⁴ The major component of skin is type I collagen – hence, unless specified otherwise, here the term ‘collagen’ will always refer to type I collagen. Other collagens do feature in leather making, however, and their roles are defined later.
Collagens are proteins, that is, they are made up of amino acids. They can be separated into the α-amino acids and the β-amino acids, as shown in Figure 1.1. Each one features a terminal amino group and a terminal carboxyl group, which become involved in the peptide link (see later), and a sidechain attached to the methylene group in the centre of the molecule. When the amino acids are linked together to form proteins, they create an axis or ‘backbone’ to the polymer, from which the sidechains extend. It is the content and distribution of the sidechains that determine most of the properties of any protein. In the case of collagen, it is the sidechains that largely define its reactivity and its ability to be modified by the stabilising reactions of tanning. In addition, the chemistry of the backbone, defined by the peptide links, offers different reaction sites that can be exploited in some tanning processes.
Figure 1.1 Amino acid structures, α and β.
All the common amino acids are found in skin or skin components. There are two notable aspects of the amino acid content of collagen. Hydroxyproline, represented in Figure 1.1, is almost uniquely present in collagen compared with other proteins, therefore offering the basis of measuring the collagen content in any skin or skin derivative. Tryptophan, shown in Figure 1.2, is absent, therefore making collagen deficient as a foodstuff.
Figure 1.2 Tryptophan.
In terms of leather making, some amino acids are more important than others, since they play defined roles, set out in Table 1.1: the roles of importance are either in creating the fibrous structure or involvement in the processing reactions for protein modification. Other amino acids, not included in the table, are important in defining the properties of the collagen, but play less defined roles in the leather-making processes.
Table 1.1 Amino acids of importance in leather making
aIn biology, referred to as pI.
Amino acids create macromolecules, proteins such as collagen, by reacting via a condensation process as shown in the following equation, where the amide or peptide link is in bold:
The condensation reaction, removing the elements of water, can be reversed by hydrolysis, by adding the elements of water. Clearly, hydrolysis, as set out in this equation, cannot be fast, nor does the equilibrium lie to the left, otherwise the protein would be unstable and useless as the basis of life. On the other hand, the hydrolysis reaction is catalysed by general acid and general base; importantly for leather making, it is catalysed by H+ and OH−. The impact on processing can be illustrated in the following way.
In the earliest stage of processing, hair is usually removed and at the same time the skin
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