Mold and Core Sands in Metalcasting: Chemistry and Ecology: Mariusz Holtzer Angelika Kmita

Mariusz Holtzer
Angelika Kmita
Mold and
Core Sands in
Metalcasting:
Chemistry and
Ecology
Sustainable Development
Mold and Core Sands in Metalcasting: Chemistry
and Ecology
Mariusz Holtzer • Angelika Kmita
Mold and Core Sands

in Metalcasting: Chemistry
and Ecology
Sustainable Development
Mariusz Holtzer Angelika Kmita
AGH University of Science and Technology AGH University of Science and Technology
Krakow, Poland Krakow, Poland
Translated by Janina Pawlikowska-Czuba
ISBN 978-3-030-53209-3 ISBN 978-3-030-53210-9 (eBook)

https://doi.org/10.1007/978-3-030-53210-9
© Springer Nature Switzerland AG 2020

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Preface
Foundry industry is a key factor in the economy of several countries. At the same
time, foundry operations, by generating harmful gases and vast amounts of waste,
are increasing environmental pollution. During the last 15–20 years, the negative
effect of foundry was more evident when molding sands with chemically bound
binders were introduced. This plight was forced by customers who required castings
of improved surface quality, higher dimensional accuracy, decreased walls thick-
ness, and better efficiency from foundries. This led to a wide-scale application of
castings in fields such as motorization, space and armaments industries. On the
other hand, due to increasing societal pressure and administrative requirements,
foundries are forced to employ effective technologies for molding sands using bind-
ing materials. For example, using geopolymer binders or water glass–based inor-
ganic binders hardened by physical factors, e.g., temperature. However, these
inorganic binders have limited applications and depend on dimensions of cores and
molds, temperatures of pouring metals, or matrix types. Molding sands with ben-
tonite (green sands) and with additions generating lustrous carbon will be still dom-
inating the production of iron castings. However, it seems that some more time is
required to produce molding sands with chemically bound binders or with bentonite
(green sands) with limited or without harmful carbon additives.
A good casting depends on two elements: proper sand mold and liquid metal
with desired properties and composition. The quality of these two elements deter-
mines the quality of the obtained casting. Compared with research carried out for
melting of metals, inoculation, refining, or spheroidizing of metal alloys, research
concerning chemical and physicochemical processes and gases evolved during
hardening or destruction of molding sands under high temperature.
To a certain degree, the book should fill this gap. In addition, harmful effects of
molding and core sands, their historical trail, their preparation, processes of making
molds and cores, pouring liquid metal into molds, and knocking out castings are
discusses in this book. Simultaneously, readers’ attention was drawn to environ-
mental impacts of spent foundry sands. Authors also attempt to accurately describe
reactions occurring in sands during their hardening and thermal degradation, but
this was not always possible due to high complexity of these processes. Several
v
vi Preface
relevant research and their investigation results for molding and core sands – regard-
ing their harmful effects for employees and the environment – are mentioned in
this book.
As molding sands use chemically bound binders, authors decided to include a
short course on organic chemistry and the bases of the polymerization process.
We expect this book will allow its readers to understand better about phenomena
and processes in casting production, especially related to molding sands. Therefore,
novel – not much harmful – binders for molding and core sands are introduced in
this book.
We hope this book will be a useful source of information for students, scientists,
academicians, research scholars, and foundry engineers.
Special thanks are directed toward MSc Joanna Kuciakowska and Dr Agnieszka
Roczniak for their help in the preparation of this book for printing.
We would like to express our gratitude to the reviewers Prof. Józef Dańko and
Prof. Andrzej Baliński, who provided their valuable comments and suggestions for
this book.
Krakow, Poland, 08.2020 Mariusz Holtzer

Angelika Kmita
Abbreviations
AC Amorphous carbon
ADV Acid demand value
AFS American Foundryman Society
AOP Advanced oxidation process
Ar Aromatic group
BAT Best Available Techniques
BMGVs Biological monitoring guidance values
BOELV Occupational exposure
BS Benzene sulfonic acid
BTEX Benzene, toluene, ethylobenzene, xylenes
CAS Chemical Abstracts Service (Registry Number)
CAAA Clear Air Act Amendments
CERP Casting Emissions Reduction Program
CT Coagulation threshold
DMEA Dimethylethylamine
DMPA Dimethylpropylamine
DMIPA Dimethylisopropylamine
DNA Deoxyribonucleic acid
DSC Differential scanning calorimetry
EU European Union
EPS Expanded polystyrene
FA Furan (resin)
FC Fugacit carbon
FMP Full-mold process
FNB Furan no-bake
FRC Free radical curing
FTIR Fourier transform infrared spectroscopy
GC/MS Gas chromatography/mass spectrometry
GC Gas chromatography
HAP Hazardous air pollutant
HMTA Hexamethylenetetramine
vii
viii Abbreviations
IARC International Agency of Research on Cancer

IOELV Occupational exposure limit values
IUPAC International Union of Pure and Applied Chemistry
KS Sulfuric acid
LAc Lactic acid
LC Lustrous carbon
LCF Lustrous carbon formers
LFP Lost-foam process
LOI Loss on ignition
MAK limit Maximal concentration of chemical substances at the work place
MDI Methylene diphenyl diisocyanate
MMA Methyl methacrylate
NDS Occupational limit
NDSCH Exposure limit
NDSP Highest permissible threshold concentration
OSHA PEL Permissible exposure limits
OTS o-Toluenosulfonic acid
PAHs Polycyclic aromatic hydrocarbons
PCDD Polychlorodibenzodioxine
PCDF Polychlorodibenzofuranes
PCB Polychlorinated biphenyls
PCL Polycaprolactam
R Alkyl group
SFS Spent foundry sand
PEVA Polyethylene vinyl acetate
PF-FA Phenol-formaldehyde–furfuryl alcohol
PGA Poly(glycolic acid)
PLA Poly(lactic acid)
ppm parts per million
PTS p-Toluene sulfonic acid
PU Phenolic urethane
PUCB Phenolic urethane cold-box
PUNB Phenolic urethane no-bake
REACH Registration, Evaluation, Authorization and Restriction of
Chemicals
R–FA Resorcinol–furfuryl alcohol
RNA Ribonucleic acid
RP Rapid prototyping
RT Rapid tooling
RM Rapid manufacturing
STEL Short-term exposure limits
TCLP Toxicity characteristic leaching procedure
TDI Toluene-2,4-diisocyanate
TEA Triethylamine
TEOS Tetraethyl orthosilicate
Abbreviations ix
TGA Thermogravimetric analysis

TLV Threshold limit value
TLV–TWA Threshold limit value–time-weighted average
TLV–STEL Threshold limit value–short-term weighted average
TLV–C Threshold limit value–ceiling limit
TMA Trimethylamine
TWA Time-weighted average
US EPA United States Environmental Protection Agency
UF–FA Urea-formaldehyde–furfuryl alcohol
UF–PF–FA Urea-formaldehyde–phenol resin–furfuryl
WEL–TWA Workplace exposure limits–time-weighted average
WEL–SHORT Workplace exposure limits–short-term weighted average
VOC Volatile organic compounds
XSA Xylene sulfonic acid
Contents
1 Introduction�� 1
References�� 10
Part I Organic Chemistry

2 General Principles of Organic Chemistry �� 15
2.1 Organic Compounds: Structure and Bonding �� 15
2.2 Organic Chemical Reactions: Classifying�� 16
2.3 Hydrocarbons�� 18
2.3.1 Alkanes �� 18
2.3.2 Alkenes �� 23
2.3.3 Alkynes �� 25
2.3.4 Cycloalkanes�� 27
2.3.5 Cycloalkenes�� 29
2.3.6 Aromatization and Benzene�� 30
2.4 Hydrocarbons with Functional Groups�� 36
2.4.1 Alcohols and Phenols �� 36
2.4.2 Ethers�� 45
2.4.3 Aldehydes and Ketones�� 46
2.4.4 Carboxylic Acids�� 48
2.4.5 Esters of Carboxylic Acids �� 52
2.4.6 Nitrogen Organic Compounds�� 56
2.4.7 Sulfuric Organic Compounds �� 61
2.5 Polymers and Polymerization �� 62
2.5.1 Polymers and their Properties�� 62
2.5.2 Polymerization: Kinds and Mechanisms�� 65
2.5.3 Inorganic Polymers �� 72
2.5.4 Inorganic–Organic and Organo-Metallic Polymers�� 73
2.5.5 Degradable Polymers�� 74
2.5.6 Natural Polymers (Biopolymers)�� 78
References�� 82
xi
xii Contents
3 Synthetic Resins �� 83

3.1 Alkyd Resins�� 83
3.2 Phenol–Formaldehyde Resins�� 84
3.3 Phenol–Urethane Binder System�� 97
3.4 Furan Resins�� 101
3.5 Urea–Formaldehyde Resins�� 105
References�� 107
Part II Organic Binder Systems of Molding and Core Sands

4 Aggregate Molding Materials �� 113
4.1 Silica Sand�� 113
4.2 Zircon Sand�� 118
4.3 Olivine Sand�� 121
4.4 Chromite Sand�� 122
4.5 Other Minerals Used as Matrices�� 123
4.6 Synthetic Sands�� 125
Appendix 4.1�� 127
5 Division of the Molding and Core Sands: Criteria �� 129
6 Cold-Setting Processes (No-Bake)�� 145
6.1 Furan Acid Catalyzed�� 145
6.2 Phenolic–Urethane No-Bake System (PUNB) �� 162
6.3 Resol Ester Hardened (ALPHASET)�� 168
6.4 Alkyd Oil, No-Bake�� 178
7 Gas-Hardened Processes (Cold-Box) �� 185
7.1 SO2 Hardened Furan Resins (HARDOX) �� 185
7.2 Amine Hardened Phenolic–Urethane Cold-Box (PUCB)�� 186
7.3 Alkaline Phenolic Methyl Formate Hardened (BETASET)�� 198
7.4 CO2 Hardened Alkaline Phenolic�� 200
7.5 SO2 Hardened Epoxy/Acrylic (Free Radical Curing) (FRC)�� 202
8 Heat Curing Processes �� 205
8.1 Linseed Oil Oven Bake �� 205
8.2 Warm-Box Process�� 206
8.3 Hot-Box Process, Phenolic or Furan-Based�� 208
8.4 Croning Process (Shell Process) �� 212
Contents xiii
Part III Inorganic Binder Systems of Molding and Core Sands and

Protective Coatings
9 Sodium Silicate Molding Sands�� 219
9.1 Sodium Silicate: Structure and Physical–Chemical Properties�� 221
9.2 Hardening of Molding Sands with Sodium Silicate �� 225
9.2.1 Molding Sands Hardened by Chemical Agents�� 225
9.2.2 Molding Sands Hardened by Physical Factors �� 229
9.2.3 Sodium Silicate Modification �� 234
10 Green Sands�� 243
10.1 General Characteristics of Green Sands �� 243
10.2 Bentonite: Structure and Properties�� 245
10.3 Additions Generating Lustrous Carbon�� 251
10.4 Water and its Role in Green Sands�� 257
10.5 Thermophysical Properties of Green Sands�� 258
10.6 Rebounding and Reclamation of Green Sands �� 260
10.7 Limitations of Negative Influences of Green Sands on the
Environment and Work Conditions�� 267
11 Other Molding and Core Sands with Inorganic Binders �� 277
11.1 Geopolymer Binder�� 277
11.2 Water-Soluble Cores �� 279
12 Protective Coatings for Mold and Core Sands�� 285
Part IV Special Technologies of Making Molds and Cores

13 Alternative Methods Using in Mold and Core Technologies�� 297
13.1 Evaporative-Pattern Casting�� 297
13.1.1 Materials for Evaporative-Pattern Casting�� 298
13.1.2 Coats for Evaporative Patterns�� 301
13.2 Lost Foam Process (LFP)�� 302
13.3 Full-Mold Process (FMP) �� 305
13.4 Ceramic Shell�� 306
13.4.1 Shaw’s Method �� 307
13.4.2 Investment Casting�� 309
13.5 Vacuum Molding (V-Process) �� 314
13.6 Frozen Mold�� 316
13.7 Rapid Prototyping Technology �� 318
13.8 Natural Polymer-Based Composite Binders �� 321
13.8.1 α-Starch-Based Binders�� 321
13.8.2 Collagen-Based Composite Binders �� 322
xiv Contents
13.8.3 Binder Based on Polysaccharide�� 324

13.9 Synthetic Polymer-Based Composite Binders�� 324
Part V Environmental Aspects Mold and Core Technologies

14 Influence of the Technology of Molding and Core Sands on the
Environment and Working Conditions: Summary�� 333
14.1 Emission of Harmful Substances from Molding and Core
Sands �� 333
14.2 Influence of Spent Molding and Core Sands on the
Environment�� 337
14.3 After Reclamation Dusts and their Influence on the
Environment�� 342
Index�� 347
About the Authors
Mariusz Holtzer Ph.D., is currently Full Professor at

AGH-University of Science and Technology, Faculty
of Foundry Engineering, Krakow, Poland.
Professor M. Holtzer graduated from the Jagiellonian
University, Department of Chemistry, Krakow. His
research activities are focused on the following areas:
physical chemistry of metallurgical and foundry phe-
nomenon on the interface of the liquid metal – ceramic
material, the construction of metallurgical slags, issues
related to limiting the negative impact of foundry
industry on the environment, waste management, new
ecological binders for molding and core sands, hazard
evaluation of materials used in foundry, and modern
analytical methods such as Py/GC/MS, TG/MS, and
TG/DTG/FTIR/MS.
Professor M. Holtzer has participated in 16 scientific
and industrial projects as project manager or a co-
worker. He has edited over 8 books and published over
300 scientific papers. He has coauthored over 14 pat-
ents (US and EU) and patent applications. He has
authored two monographs: Metallurgical and Foundry
Processes of Iron Alloys: Physicochemical
Fundamentals (2013) (in Polish) and Microstructure
and Properties of Ductile Iron and Compacted Graphite
Iron Castings: The Effects of Mold Sand/Metal Interface
Phenomena (2015) (in English).
xv
xvi About the Authors
Angelika Kmita is currently an Assistant Professor

at AGH-University of Science and Technology,
Academic Centre for Materials and Nanotechnology,
Krakow, Poland. Her research activities are focused
on the following areas:
(a) Synthesis of ferrite nanoparticles with controlled
morphology and size;
(b) Synthesis of magnetic fluids (ferrofluids);
(c) Synthesis of multifunctional hybrid
nanocomposites;
(d) Examination of the magnetic hyperthermia of
the aqueous solutions of nanoparticles;
(e) Investigation of rheological properties of
materials;
(f) Modification of binders for molding and core
sands by nanoparticles;
(g) Topics related to environmental protection prob-
lems in the foundry industry.
Dr A. Kmita has participated in 11 scientific and
industrial projects (as project manager or co-worker).
She has co-authored over 40 scientific publications
(e.g., in Inorganic Chemistry, Composites Part B
Engineeing, Applied Thermal Engineering, Journal of
Materials Chemistry C, Materials, Nanoscale etc.),
and has co-authored three monographs as well as three
patents.
List of Figures
Fig. 1.1 Sources of emission of compounds from the HAP group

in the iron alloy foundry. (Adapted from Ref. [12])�� 4
Fig. 2.1 Schematic division of hydrocarbons�� 19
Fig. 2.2 The characteristic reaction of aromatic hydrocarbons�� 32
Fig. 2.3 Oxidation of aromatic hydrocarbons�� 33
Fig. 2.4 Derivatives of carboxylic acid�� 52
Fig. 2.5 Basic division of polymers, adapted from [15]�� 63
Fig. 2.6 Dependence of the polymerization degree on the conversion
degree of the chain polymerization (curve 1) and gradual
polymerization (curve 2). (Adapted from Ref. [16])�� 64
Fig. 2.7 Thermal decomposition of dibenzoyl peroxide�� 67
Fig. 2.8 Formation of polystyrene�� 68
Fig. 2.9 The anionic polymerization course at the example of styrene�� 69
Fig. 2.10 Schematic presentation of the poly(lactic acid) formation
by the polymerization method with opening the lactide ring�� 75
Fig. 2.11 Schematic presentation of the poly(lactic acid) formation
by the polycondensation of lactic acid�� 75
Fig. 2.12 Curves of the thermal decomposition of selected polymers
(PP, polypropylene; PE, polyethylene; PS, polystyrene; PVC,
polyvinylchloride) [16]�� 77
Fig. 3.1 Polymerization of alkyd resin with using phthalic acid
anhydride, glycerine, and fatty acid�� 84
Fig. 3.2 Scheme representing polycondensation of phenol and
formaldehyde to obtain various products of this reaction,
depending on the reaction conditions. (Reprinted by
permission from Ref. [12])�� 88
Fig. 3.3 Schematic presentation of the polymerization process
course of novolak and resol phenol resins�� 88
Fig. 3.4 Scheme of the phenol and formaldehyde connection�� 88
Fig. 3.5 Scheme of the formation of hydroxyl derivatives in the
reaction of phenol with formaldehyde�� 89
xvii
xviii List of Figures
Fig. 3.6 Condensation of hydroxyl derivatives�� 89

Fig. 3.7 Formation of the ether bond as the result of condensation of
hydroxyl derivatives�� 89
Fig. 3.8 Possibility of forming methylene bridge (−CH2−) in ortho- or
para- position aromatic ring. (Adapted from Ref. [19])�� 90
Fig. 3.9 Formula of hexamethylenetetramine and the structure of
cross-linked novolak resin (formation of methyleneamine
bridges). The hardening process occurs in two stages�� 91
Fig. 3.10 Cross-linking of novolak resin in the hexamine presence.
(Reprinted by permission from Ref. [20])�� 92
Fig. 3.11 Structure of cross-linked phenol–formaldehyde resol resin�� 93
Fig. 3.12 Possible reactions occurring at the thermal degradation of PF
resin. (Adapted from Ref. [31])�� 96
Fig. 3.13 Polyurethane synthesis�� 98
Fig. 3.14 General equation of forming the urethane group. (Reprinted
by permission from Ref. [12])�� 99
Fig. 3.15 Examples of the most often applied aromatic diisocyanates�� 99
Fig. 3.16 Scheme of the synthesis of diisocyanates (without phosgene)�� 100
Fig. 3.17 Raw materials for production of furan resins�� 101
Fig. 3.18 Obtaining of furfuryl alcohol and furan from raw plant
materials. (Adapted from Ref. [50])�� 102
Fig. 3.19 World utilization of furfuryl alcohol in 2015. (Reprinted by
Fig. 3.20 Self-condensation reaction of furfuryl alcohol�� 103
Fig. 3.21 Reaction of self-condensation of furfuryl alcohol in the acidic
environment�� 103
Fig. 3.22 Structure of phenol–formaldehyde modified by furfuryl
alcohol and hardened by p-toluenesulfonic acid. (Adapted
from Refs. [55, 56])�� 104
Fig. 3.23 Transition from furfuryl alcohol to a highly cross-linked
furan matrix in furan binder. (Adapted from Refs. [58–60])�� 105
Fig. 3.24 Two steps in formation of urea–formaldehyde resin�� 106
Fig. 3.25 Formation of mono- and dimethylol ureas in the reaction of
urea with formaldehyde (first stage)�� 106
Fig. 3.26 Polycondensation of methyl derivatives of urea with a
formation of macroparticles connected by methylene bridges.
(Adapted from Ref. [65])�� 106
Fig. 3.27 Formation of a linear polymer�� 107
Fig. 4.1 Typical grain size distribution of silica sand. (Adapted from
Refs. [1, 3])�� 115
Fig. 4.2 Thermal linear expansion characteristic of sands for molds
and cores. (Reprinted by permission from Ref. [5])�� 116
Fig. 4.3 Thermal volumetric expansion characteristics of sands for
molds and cores. (Reprinted by permission from Ref. [5])�� 116
List of Figures xix
Fig. 5.1 Fractions of green sand molding in technologies applied for

cast iron production. (Reprinted by permission from
Ref. [2])�� 130
Fig. 5.2 Typical pathway of hardening curve of self-setting sands
(Tw. work time; Ts, strip time; Tc, casting time; Tmax, time to
achieve the maximum strength). (Adapted from Ref. [12])�� 135
Fig. 5.3 Technologies applied in EU for producing molds and cores
(a) and technologies of producing cores with chemically
bonded sands (b). (Adapted from Refs. [1, 15])�� 137
Fig. 5.4 Air emission sources during preparing of sands and producing
castings. (Reprinted by permission from Ref. [26])�� 141
Fig. 5.5 Comparison of gas evolution rates of sands with organic and
inorganic binders and for green sands: Sinotherm®, alkaline
phenolic resole resin; Kalltharz X 850®, furan resin; Geopol®
and Rudal®, inorganic binders. (Reprinted by permission from
Ref. [29])�� 142
Fig. 6.1 Thermal decomposition of p-toluenesulfonic acid [8]�� 149
Fig. 6.2 Polymerization reaction of furan resin�� 150
Fig. 6.3 Influence of a sulfur content in a binder on its amount in a
reclaim: (red line, low-sulfur binder; black line, high-sulfur
binder). (Reprinted by permission from Ref. [13])�� 152
Fig. 6.4 Influence of nitrogen content in a binder on its amount in a
reclaim: (red line, low-nitrogen binder; black line, high-nitrogen
binder). (Reprinted by permission from Ref. [13])�� 152
Fig. 6.5 Overlay reaction pathways for the formation of aromatic
compounds in pyrolysis of the furan binder cured with
p-xylene sulfonic acid. (Adapted from Refs. [16–18])�� 154
Fig. 6.6 Scheme formation of aromatic compounds from the PAHs
group by pyrolysis process (Reprinted by perrmission from
Ref. [17]) Hydrogen–abstraction/acetylene–addition (HACA)
mechanism accelerate the formation polycyclic aromatic
hydrocarbons (PAHs) like pyren from naphthalene�� 156
Fig. 6.7 Structure of phenol–urethane binder�� 162
Fig. 6.8 Differences in structures of binders applied in the PUNB
and PUROLiTe technology. (Reprinted by permission from
Ref. [37])�� 164
Fig. 6.9 Emission of VOC and formaldehyde from molding sand with
polyurethane (PUNB) and PUROLiTe binder during making
cores by means of shooting machine (0.8% of resin and 0.8%
of activator). (Reprinted by permission from Ref. [37])�� 167
Fig. 6.10 Leaching of organic compounds into the environment from
spent sands (PUNB and PUROLiTe) during their storing
(0.8% of resin and 0.8% of activator); limits for individual
classes of wastes valid in Germany. (Reprinted by permission
from Ref. [37])�� 167
xx List of Figures
Fig. 6.11 Hydrolysis reaction of ester in a basic environment�� 170

Fig. 6.12 Reaction of the ester (hardener/catalyst) with −CH2O group
from the resin�� 171
Fig. 6.13 Quinone methide is an active intermediate substance,
facilitating hardening of alkaline phenol resin�� 171
Fig. 6.14 General scheme of the reaction of phenol–formaldehyde resin
with ester�� 172
Fig. 6.15 Structure of polymerized alkaline phenol–formaldehyde resin
hardened by esters�� 175
Fig. 6.16 Py/GC/MS chromatogram obtained as a result of the “flash”
pyrolysis of the commercial resin used in the ALPHASET
technology at 700 °C [72]�� 178
Fig. 7.1 Structural formulae of amines applied in the cold-box process�� 187
Fig. 7.2 Components of binder for cold-box technology�� 189
Fig. 7.3 Toluene diisocyanates used in cold-box technology�� 189
Fig. 7.4 Reaction of the cold-box process with using polyisocyanate�� 190
Fig. 7.5 Hardened polyurethane binder�� 190
Fig. 7.6 Solvents applied in the cold-box technology in a historical
perspective. (Adapted from Refs. [13, 14])�� 194
Fig. 7.7 Comparison of odor emissions from the cold-box technology,
measured at the hood stack outlet in the aluminum alloys
foundry. Both technologies (traditional and TEOS) contained
equivalent amounts of a binder. (Reprinted by permission
from Refs. [23, 24])�� 195
Fig. 7.8 Structure cold-box resin of the 5th generation. (Adapted
from Ref. [13])�� 195
Fig. 7.9 Reactions during curing of the mold sands (BETASET process).
Fig. 7.10 Resin cross linking after CO2 introduction (resole–CO2 process).
Fig. 8.1 Structure of cross-linked of unsaturated fatty acids�� 206
Fig. 8.2 Comparison of volumes of gases emitted at a temperature of
800 °C from molding sands prepared according to the
hot-box and warm-box technologies. (Reprinted by
Fig. 8.3 Scheme of the hot-box process: core making. (Adapted from
Ref. [7])�� 209
Fig. 8.4 Scheme of the curing of PF novolak resin in the hot-box plus
process (HTMA – hexamethylenetetramine)�� 210
Fig. 8.5 Scheme of the curing of furfuryl resin in the hot-box process�� 211
Fig. 9.1 Preparation of sodium silicate. (Adapted from Refs. [1, 18])�� 221
Fig. 9.2 The reaction of hydrolysis of sodium silicate�� 221
List of Figures xxi
Fig. 9.3 Reaction of sodium silicate activation. (Adapted from

Refs. [1, 18])�� 222
Fig. 9.4 The condensation reaction by dehydration. (Adapted from
Refs. [1, 18])�� 222
Fig. 9.5 Increase of sodium silicate particles by multiple
condensation – formation of spatially branched chains.
(Adapted from Refs. [1, 18])�� 222
Fig. 9.6 Decomposition reaction of sodium silicate as a result of the
siloxane (Si–O–Si) bond hydrolysis. (Adapted from Refs. [1,
18])�� 223
Fig. 9.7 The reaction of deactivation of sodium silicate. (Adapted
from Refs. [1, 18])�� 223
Fig. 9.8 Stages of monomer polymerization and particle formation
according to R. K. Iler [19]�� 223
Fig. 9.9 A simplified model of the micelle. (Adapted from Ref. [21])�� 224
Fig. 9.10 Scheme sol ↔ gel transition�� 225
Fig. 9.11 Changes of the final compression strength (Rctk) at the
temperature increase: molding sand with sodium silicate
hardened by CO2. (Adapted from Refs. [3, 35])�� 227
Fig. 9.12 Mechanism of bonding of hydrated sodium silicate in the
esterification process according to [3] (a) ester hydrolysis,
(b) dissociation of acetic acid, and (c) reaction of acetic
anions with sodium silicate. (Adapted from Refs. [3, 38])�� 228
Fig. 9.13 Changes of the final compression strength (Rctk) at the
temperature increase: molding sand with sodium silicate
hardened by esters. (Adapted from Refs. [3, 35])�� 229
Fig. 9.14 INOTEC® binder composition. (Adapted from Ref. [41])�� 231
Fig. 9.15 Comparison of the condensate volume for the CORDIS®
binder with other binders (temperature of liquid aluminum
alloy: 700 °C). (Reprinted by permission from Ref. [13])�� 232
Fig. 9.16 Schematics of bond formation by AWB® binder. (Reprinted
Fig. 9.17 Comparison of knocking out properties (knockout work Lw
value) of molding sands with sodium silicate modified by
alcoholic solutions of nanoparticles [49]�� 237
Fig. 10.1 Crystal structure of montmorillonite. (Adapted from Refs. [11,
12])�� 246
Fig. 10.2 (a) A silica tetrahedron in which the central silicon ion is
coordinated to four oxygen ions (bright balls are oxygen atoms
and black balls are silicon cations). (b) An alumina octahedron
in which the central aluminum ion is coordinated to six
hydroxyls (black balls are hydroxyls, and small gray balls are
cations with octahedral coordination Al, Fe, Mg). (Adapted
from Ref. [13])�� 247
xxii List of Figures
Fig. 10.3 Cis- and trans isomers in the octahedral structure of bentonite.
Fig. 10.4 Structure of montmorillonite, 1 Å = 10−8 m. (Reprinted by
Fig. 10.5 (a) Oxidation atmosphere in the mold cavity before pouring
with molten metal. (b) Emission of lustrous carbon from
gaseous phase on cooler surfaces. (Reprinted by permission
from Ref. [14])�� 253
Fig. 10.6 Formation of benzene from sea coal dust (pyrolysis,
dehydration, and condensation). (Adapted from Ref. [28])�� 253
Fig. 10.7 Reactions in result of which the reducing atmosphere is
formed in a mold�� 253
Fig. 10.8 Influence of salt (NaCl) on the bentonite activity. Salt
deactivates electrostatic bonds of bentonite. (Reprinted by
Fig. 10.9 Structure of the heated surface of a green sand mold, against
a steel casting, and the forms of silica (after Sosman R.R. 1927)
with solid lines denoting stable states and broken lines denoting
unstable states. (Reprinted by permission from Ref. [4])�� 259
Fig. 10.10 Schematic presentation of distribution of devices in the
foundry using green sands. (Reprinted by permission from
Refs. [16, 43])�� 261
Fig. 10.11 Bridge between sand grains in green sands. (Reprinted by
|permission from Ref. [14])�� 263
Fig. 10.12 Dependence of the water boiling temperature on the outside
pressure�� 264
Fig. 10.13 Molding sand preparation plant with vacuum mixer-cooler.
(Reprinted by permission from Refs. [16, 47])�� 265
Fig. 10.14 Comparison of green sands, with no carbon, with sea coal,
|and with lignite. (Reprinted by permission from Ref. [3])�� 267
Fig. 10.15 Effect of increasing lignite: sea coal ratio on (a) benzene
emissions and (b) toluene emissions. (Reprinted by permission
from Ref. [3])�� 270
Fig. 11.1 Diagram of the structure of geopolymer: tetrahedrons SiO44−
and AlO45−. (Adapted from Ref. [3])�� 278
Fig. 11.2 Results of pollutants (BTEX and PAHs) measurement during
pouring, comparison of organic and inorganic binder systems.
Fig. 12.1 Comparison of the surface quality of iron casting with and
without protective coatings at different metallostatic pressures
( “O”, samples without protective coating; “1,” samples with
commercial protective coating; “2” and “3” – samples with
experimental protective coating). (Reprinted from Ref. [13])�� 290
List of Figures xxiii
Fig. 13.1 Formation of polystyrene�� 298

Fig. 13.2 Formation of polymethyl methacrylate�� 298
Fig. 13.3 TGA and DTG curves of polystyrene in 1, air and 2, nitrogen
atmosphere. Ta, temperature of the polymer decomposition
beginning and Tmax, maximum temperature on the DTA curve,
in which the polymer decomposition rate is the highest. An
exothermic peak also appears at this temperature. (Reprinted
Fig. 13.4 FTIR spectra of volatile products of styrene thermal
decomposition in the air atmosphere (decomposition
temperature: 1, 300 °C; 2, 400 °C; 3, 500 °C; 4, 600 °C).
Fig. 13.5 Main decomposition products of the polystyrene macro
molecules. (Adapted from Ref. [11])�� 302
Fig. 13.6 The lost foam process (LFP). (Reprinted by permission from
Refs. [20, 21])�� 303
Fig. 13.7 Structure of ethyl silicate (ethylene groups are bound with
silicon atom by oxygen bridges)�� 308
Fig. 13.8 Scheme of the investment casting process. (Reprinted by
permission from Refs. [20, 21])�� 310
Fig. 13.9 Stages of vacuum forming. (Reprinted by permission from
Refs. [21, 53])�� 315
Fig. 13.10 Schematic illustration of the differential pressure mold
freezing method. (Reprinted by permission from Ref. [60])�� 317
Fig. 13.11 High-temperature stress-strain curves of cores manufactured
with binder containing α-starch. (Reprinted by permission
from Ref. [75])�� 322
Fig. 13.12 Hot distortion test for cores manufactured with several types
of binders. (Reprinted by permission from Ref. [75])�� 323
Fig. 13.13 Scheme manufacturing PLA as a polymerization result of
lactide�� 325
Fig. 13.14 Scheme manufacturing PLA by polycondensation lactic acid�� 325
Fig. 13.15 Lactic acid production on an industrial scale�� 325
Fig. 13.16 Preparation of polycaprolactone�� 325
List of Tables
Table 1.1 The largest producers of castings in the world (data for 2018)�� 2
Table 1.2 Indicative exposure limit values applied in Poland and other
countries for compounds emitted in casting process�� 6
Table 2.1 Classification of organic compounds on the bases of functional
groups�� 17
Table 2.2 Simplified formulas, names, and symbols of abbreviations of the
selected hydrocarbon groups�� 20
Table 2.3 The alkanes homologous series�� 23
Table 2.4 The homologous series of alkenes�� 24
Table 2.5 The homologous series of alkynes�� 26
Table 2.6 The homologous series of cycloalkanes�� 28
Table 2.7 The homologous series of cycloalkenes�� 29
Table 2.8 Physical properties and structures of aromatic hydrocarbons
from BTEX group�� 34
Table 2.9 Physical properties and the structure of the selected substances
from PAHsa group�� 37
Table 2.10 Examples of aliphatic and aromatic ethers�� 46
Table 2.11 Examples of carboxylic acids (monocarboxylic acids)�� 50
Table 2.12 Comparison of the gradual and chain polymerization�� 72
Table 3.1 Properties of phenol [6]�� 85
Table 3.2 Properties of formaldehyde [6]�� 86
Table 3.3 Processes of molds and cores production in which
phenol–formaldehyde resin is used�� 95
Table 4.1 Recommended chemical composition of silica sand applied in
castings�� 114
Table 4.2 Recommended physicochemical properties of silica sands
applied in foundries�� 115
Table 4.3 Grain composition of typical silica sands applied in Germany
and Great Britain�� 117
Table 4.4 Basic properties of sands use for making of molds and cores�� 119
Table 4.5 Chemical composition of zircon sand (mas.%)�� 121
xxv
xxvi List of Tables
Table 4.6 Chemical composition of typical olivine sand (mas.%)�� 121

Table 4.7 Grain analysis of olivine sand (mas.%)�� 122
Table 4.8 Chemical composition of typical chromite sand (mas.%)�� 123
Table 4.9 Chemical composition of silica sand and Fe–Cr slag (%) [19]�� 124
Table 4.10 Chemical composition of CERABEADS® synthetic sand (%)�� 125
Table 4.11 Grain size distribution of CERABEADS® synthetic sand�� 126
Table 5.1 Fractions of individual technologies of making molding and
core sands in the foundry industry of EU and the USA�� 131
Table 5.2 Resins applied for production of molds and cores as well as the
possibility of their using for the given casting alloy�� 136
Table 5.3 Consumption of various resins, catalysts, hardeners, and
additions at preparing chemically bond sands�� 138
Table 5.4 History of mold and core making processes�� 140
Table 5.5 Emission coefficients during thermal decomposition of selected
organic binders�� 141
Table 5.6 Emission of dangerous substances from molding sands (total
dust, PAHs, B(a)P)�� 142
Table 6.1 Hardeners used in molding sands with furan resins�� 147
Table 6.2 Emission of compounds of the BTEX and HAP groups from
molding sands with furan resin (containing 25% of free furfuryl
alcohol) hardened by various hardeners (the sand sample
was poured with cast iron of a temperature of 1350 °C)�� 157
Table 6.3 Concentration of PAHs which released during the thermal
decomposition of molding sands with furan resin with different
contents of free furfuryl alcohol�� 157
Table 6.4 Analyses of gases emitted from molds made of molding
sands with furan resin hardened by sulfonic acids�� 158
Table 6.5 Emission of BTEX gases from molding sands made on
matrices with various fractions of the reclaim (100SP, matrix,
100% of fresh sand; 50SP50R, 50% of fresh sand +50% of
reclaim; 100R, matrix, 100% of reclaim) (sand composition:
urea–formaldehyde resin modified by furfuryl alcohol, 1.0%;
hardener, 0.5%)�� 159
Table 6.6 Emission of PAHs from molding sands made on matrices with
various fractions of the reclaim�� 159
Table 6.7 Effect of reclaim addition on leaching of substances from
molding sand with furan resin�� 161
Table 6.8 Esters used as hardeners in the ALPHASET process and their
properties�� 169
Table 6.9 Influence of the amount of ester hardener of a medium
hardening rate (glycerol triacetate +1,4 butyrolactone) on the
tensile strength of molding sand from the ALPHASET
technology�� 170
List of Tables xxvii
Table 6.10 Obtained levels of molding silica sand reclamation, based for
selected technologies [64]�� 172
Table 6.11 Comparison of physical properties of fresh olivine sand, its
reclaim after mechanical and thermal reclamation�� 174
Table 6.12 Emission of gases from molding sand with alkaline resol resin
(ALPHASET) and with furan resin�� 176
Table 6.13 Characteristic of the molding sand before pouring with molten
metal�� 176
Table 6.14 Emission of compounds from the BTEX group released during
pouring of the cores from ALPHASET technology with cast
iron and aluminum alloy AK 11�� 176
Table 6.15 Emission of compounds from the PAH group (sample of
molding sand pouring by cast iron, matrix – quartz sand)
(sampling according to the methodology described in [69])�� 177
Table 6.16 List of the identified gases released during pyrolysis, at 500 and
700 °C, from commercial resin used in the APLHASET
technology [72]�� 179
Table 6.17 Results of the analysis of gases from the BTEX group released
from molding sand with alkyd binder (alkyd resin +
polyisocyanate) (Commercial resin: A, B, and C come from
different manufacturers) during semi-technical scale tests�� 180
Table 6.18 Results of the PAHs analysis in gases emitted from the
molding sand (calculated on 1 kg of molding sand) with resin
A after pouring by cast iron at the temperature 1350 °C�� 180
Table 7.1 Properties of tertiary amines [2, 4, 7, 8]�� 190
Table 7.2 Chronological development of new generation of the cold-box
process, with taking into account the environment protection
(Huttenes-Albertus)�� 193
Table 7.3 Emission BTEX from cold-box technology�� 196
Table 7.4 Emission of PAHs from cold-box technology�� 197
Table 7.5 Physical chemical properties of resin used in BETASET
technology�� 199
Table 7.6 Emission of BTEX from resole–CO2 process, pouring with
molten cast iron and aluminum alloy�� 202
Table 7.7 Emission of PAHs (resole–CO2 process), poured with molten
cast iron�� 203
Table 8.1 Properties of urea–furfuryl resin and a catalyst applied in the
hot-box technology [13]�� 211
Table 8.2 Emission of gases from molding sand made in the hot-box
technology (PF resin + hardener + HMTA)�� 212
Table 9.1 Comparison of the tensile strength of molding sands with
sodium silicate (inorganic binder) thermally hardened and
molding sands with organic binders in dependence on
hardening time and humidity�� 220
xxviii List of Tables
Table 9.2 Parameters of cores made by various technologies�� 233

Table 10.1 Recommended properties of green sands used in the cast iron
foundry depending on the molding technique�� 245
Table 10.2 Properties of green sands applied in various parts of the world�� 245
Table 10.3 Properties of typical foundry bentonites used in various
countries and mold sands with these bentonites�� 249
Table 10.4 Substitutes of sea coal dusts�� 256
Table 10.5 Comparison of work rates before and after the replacement
of part of the coal dust mixture of graphite (savings of materials
14%, reduction of benzene emission >50%)�� 268
Table 10.6 Emission of gases from green sand with addition of different
lustrous carbon formers and content of BTEX�� 272
Table 10.7 Concentration of compounds from the PAH group in gases
emitted from the green sands and a substance forming lustrous
carbon (semi-industrial tests)�� 272
Table 10.8 Concentrations of substances from the BTEX group in gases
emitted during the thermal decomposition of a mixture of sea
coal dusts and synthetic resin, in dependence of the temperature
(decomposition in the air atmosphere) (Counted over for 1 g of
sample)�� 272
Table 11.1 Volumes of gases and concentrations of substances from the
BTEX group (mg/kg molding sands)�� 279
Table 12.1 Properties of some materials applied as matrix of coatings for
cores and molds�� 288
Table 13.1 Emissions from aluminum alloys foundry using LFP
technology and green sand (g/1 mg of liquid aluminum alloy).
(Adapted from Refs. [21, 27])�� 307
Table 13.2 Composition of the sand mold in which furan resin is
substituted by PLA or PCL�� 323
Table 14.1 List of substances identified in the air in cast iron and cast steel
foundries during the casting production�� 334
Table 14.2 Harmfulness of molding sands produced by various
technologies�� 336
Table 14.3 The chemically analysed PAH compounds in spent foundry
sands (mg kg−1)�� 339
Table 14.4 Investigation results of the elution of spent molding sands
originated from mold poured with Al alloy (T = 730 °C)
(Sample 1) and cast iron (T = 1400 °C) (Sample 2) as well as
the limit elution values, determined for wastes other than
dangerous and inert, which are not municipal wastes, allowed
to be stored in storage yards for wastes different from
dangerous and inert wastes and for inert wastes
(mg/kg of d.m.)�� 341
List of Tables xxix
Table 14.5 Basic properties of the after reclamation dusts originated

from the mechanical reclamation of molding sands with
various chemically bound binders�� 343
Table 14.6 Energetic properties and the technical analysis of dusts from
the mechanical reclamation process of molding sands with
resins (marking of dusts the same as in Table 14.5)�� 344
Chapter 1
Introduction
The foundry industry constitutes a huge and complex system of an essential influ-
ence on the economic development, social development and the environment condi-
tion, recycling application, waste utilization, and the environment improvement
[1–4]. The intensively developing foundry industry consumes large amounts of
natural resources, energy, and metals as well as generates significant amounts of
gases and solid wastes, which influence the natural environment and work condi-
tions. Therefore the adjustment of foundry plants to the sustainable development
strategy is the necessary condition of the foundry industry development [1, 4, 5].
Managers of foundry plants should realize that the responsibility for the environ-
ment and for financial results is not mutually excluding. Taking care of the environ-
ment and introducing more environment-friendly changes can cause the production
increase and its cost decrease, improve the recognition of the company name,
strengthen relations with customers, and improve profitability of the company. By
implementing the proper management of materials and wastes and applying recy-
cling, the foundry plants can matter greatly in a sustainable consumption of natural
resources. It means the necessity of taking into consideration – in strategic decision-
makings and production operations – the mutual dependence between the environ-
ment and social and economic aspects. The sustainable development is based on
innovative operations being the effect of research, i.e., of science [6]. This means
that the science is extremely important in the implementing process of sustainable
development rules. This mainly concerns working out of new innovatory sustain-
able technologies, which will contribute to materials saving and efficient energy
consumption, thus influencing favorably the environment. The world casting pro-
duction of all kinds of alloys was equal to 109.8 million Mg in the year 2017, and in
2018 this production increased to 112.7 million Mg, i.e., by 2.6%. Moreover, ten
countries were producing 87% of castings (Table 1.1).
Regardless of higher and higher expenditures on the work safety and better
devices and securities, quite often health threats and even life hazards occur in
foundry plants. During the whole production process, the employees are endan-
gered by hazardous and noxious factors related, among others, to the emission of
© Springer Nature Switzerland AG 2020 1

M. Holtzer, A. Kmita, Mold and Core Sands in Metalcasting: Chemistry and
Ecology, https://doi.org/10.1007/978-3-030-53210-9_1
2 1 Introduction
Table 1.1 The largest producers of castings in the world (data for 2018)
Country Production (Mg) Country Production (Mg)
China 49,350,000 Russia 4,200,000
India 13,399,682 Mexico 2,909,461
USA 10,756,492 South Korea 2,516,800
Japan 5,575,417 Brazil 2,283,379
Germany 5,432,999 Italy 2,261,196
Adapted from Ref. [7]
hazardous and dangerous chemical substances, air pollution, high temperatures,

noises, vibrations, and electromagnetic field. Chemical substances especially of
organic origin, present in the atmosphere, are hazardous for the employees. The
emission of inorganic dangerous substances occurs mainly during melting and
cleaning processes of castings, and mostly these substances are metal oxides.
Hazardous substances at workplaces can be gaseous, liquid, or solid. Their danger-
ous operations can take place by skin contact, breathing, or eating with food. The
main source of dust and gaseous contaminations is operations of mold pouring with
liquid metal, mold cooling, and casting knocking out. In the case of molding sands
with bentonite, these operations generate up to 90% of contaminations from the
hazardous air pollutants (HAPs) group [8–10].
According to REACH1 the binders applied in mold and core production can be
classified by their chemical composition [11]. The REACH aim is the assurance of
the high level of the human health and environment protection against chemical
hazards, promotion of alternative testing methods, increased competitiveness and
innovativeness, and ensuring the free passage of substances within the EU coun-
tries. The REACH renders the industry responsible for the evaluation and manage-
ment of the risk caused by chemical substances and for supplying the information
concerning their safety. Simultaneously the EU can require additional tests of highly
hazardous substances. The scheme of the casting production process, with marked
operations during which the danger of the HAP emission occurs, is presented in
Fig. 1.1.
The USA, on the basis of the Clear Air Act Amendments (CAAA) Title III, con-
trols the emission of 189 toxic chemical compounds encompassed by the common
name HAPs, known or suspected to be carcinogenic, occurring in various industries
and considered dangerous for the health and environment. 40 substances from this
list were occurring in the air emitted from the foundry plant, and 90% of them con-
stituted hydrocarbons. Such compounds as benzene, toluene, and xylenes domi-
nated among them (approx. 80%)2). The fraction majority in generating these
compounds has the pyrolysis of additions containing carbon (in the case of sands
1
REACH is the acronym of Registration, Evaluation, Authorization and Restriction of Chemicals.
2
Cast iron foundry having cupolas can constitute the potential source of polychlorodibenzodiox-
ines (PCDD), polychlorodibenzofuranes (PCDF), and polychlorinated biphenyls (PCB). However,
the emission coefficients of these compounds from cupolas are much lower than the emission
coefficients from incinerating plants, secondary production of non-ferrous metals, and the steel or
pig iron production [38–41].
1 Introduction 3
with bentonite) and binders (based on organic substances) applied for cores [13–
16]. For the realization of this Act in the foundry industry, the Casting Emissions
Reduction Program (CERP) was developed. This Program exists from 1994 and is
financed by the US Department of Defense. It gathers representatives from the
American Foundry Society (AFS), the Society of Foundry Materials Suppliers, and
the Department of Defense. They closely cooperate with the representatives of uni-
versities, foundry industry, suppliers of foundry materials, and the US Environmental
Protection Agency (US EPA). The main aim of the CERP program is the evaluation
of materials, equipment, and processes applied in the casting production, with
regard to their negative influence on the environment. More than 80% of castings
are produced in expendable molds prepared from sand-based matrices with addi-
tions of the proper binder. The main emission sources in the casting production
process are operations related to molding and core sands3.Certain amounts of dan-
gerous substances are emitted already at the preparation stage of molding and core
sands and at making molds and cores. Solvents, amines, and volatile organic com-
pounds (VOCs), often of unpleasant smells, should be mentioned in this place. The
polymer formed at the production of phenol–formaldehyde resin can contain not
reacted monomers of phenol and formaldehyde. Moreover, certain additions are
applied to binders to improve their humidity resistance [17]. However, the majority
of harmful substances are formed during the mold pouring with molten metal, as the
result of the high-temperature influence on binders or organic-type additions. In
dependence on the oxygen content in the atmosphere and temperature, the effect of
pyrolysis, cracking, gasification, or combustion can occur. Due to these processes,
chemical compounds which were not present in initial materials can be formed.
These substances can evaporate from molds after finishing their pouring process,
during mold cooling or casting knocking out, especially from cooler parts of cores
or molds, which were not subjected to the high-temperature influence. They can
also condense on matrix grains and remain in sands, from where they can be eluted
to the environment during spent sands storages or released at successive operations.
In dependence on the applied resin (phenol–formaldehyde, furan, furfuryl–urea,
alkyd) under the temperature influence, such substances as furfuryl alcohol, formal-
dehyde, and phenol, and from the BTEX group (benzene, toluene, ethylbenzene,
xylnes), and also polycyclic aromatic hydrocarbons (PAHs), can be formed and
released. In addition, for the molding sand hardening, the gaseous factors such as
CO2, SO2, or amines are often used. The emission potential of cores is higher than
that of molds. Therefore creating the high-quality market of foundry materials, safe
for employees and of a small negative influence on the environment, is necessary
[10, 18–24]. The atmospheric contaminations in ferrous alloys foundry plants con-
stitute complex mixtures of dusts, fumes, gases, and steams generated during vari-
ous operations. The solid fraction of contaminations is called the “ferrous foundry
particulate” (FFP). The FFP composition is very variable since it depends on the
performed production processes and applied materials (especially dangerous is the
respirable fraction of crystalline silica). The evaluation of the occupational exposure
to chemical factors occurring in the work environment is mostly based on measur-
ing or estimating the concentrations of these factors in the air and comparing them
4 1 Introduction
Fig. 1.1 Sources of emission of compounds from the HAP group in the iron alloy foundry.
(Adapted from Ref. [12])
with the assumed criteria. These criteria, also called hygienic standards and allow-
able values determine the permissible concentrations of chemical substances in the
air, in dependence on the averaging period to which they are related, known as
threshold limit value (TLV) [25].
Two time intervals are applied: long term (8 hours) and short term (15 minutes).
There are three kinds of TLV indicators, which are equivalents of the Polish indica-
tors: NDS (occupational limit), NDSCh (exposure limit), and NDSP (the highest
permissible threshold concentration)
• TLV–TWA (time-weighted average): the average exposure during 8 work hours/
day and 40 work hours/week (equivalent to NDS).
• TLV–STEL (short-term weighted average): the exposure not longer than 15 min-
utes, repeated not often than four times a day, at maintaining at least 60 minutes
break in between the exposure periods (equivalent to NDSCh).
• TLV–C (ceiling limit): the exposure value which cannot be exceeded in any
moment (equivalent to NDSP).
TLV indicators are related to chemical substances as well as to physical factors
(noise, vibration, ionizing radiation, heat, and cold).
TLV for chemical substances is expressed in ppm (parts per million), for gases,
and mg/m3, for solid particles (dusts, fumes).
1 Introduction 5
For recalculating of these units – in the case of gases – the simple equation is
used (Eq. 1.1):
mg 24.45
ppm = × (1.1)
m 3 molecular mass
In Great Britain the workplace exposure limits (WELs) determine the concentra-
tion of dangerous substances as the time-weighted average (TWA). Two time inter-
vals are applied: long term (8 hours) and short term (15 minutes) (Table 1.2). In the
European Union the workplace state is determined by several directives: Directive
(EU) 2017/164 [26] and Directive (EU) 2017/2398 [27]. Two kinds of standard
values are determined in these directives for chemical substances: indicative occu-
pational exposure limit values (IOELV) and binding occupational exposure limit
values (BOELV). The IOELV values for 123 chemical substances and BOELV val-
ues for 10 chemical substances are determined in these directives. For substances,
for which the BOELV values are determined:
• Member countries must determine their equivalent domestic values, which can
be on the same or lower level but not higher than the values determined in the
European Union.
Indicative occupational exposure allowable values according to various systems
(WEL–TWA, WEL–SHORT, TLV–Stel, TLV–TWA and TLV–C, NDS, NDSCh,
NDSP [28]) for selected chemical substances, which were found at individual stages
of the casting production process, are given in Table 1.2.
The presence of unpleasant smells (e.g., amine) decreases the work comfort;
however due to that, an earlier discovery of harmful substances in the foundry atmo-
sphere is possible (the smell threshold of substances is lower than the toxicity
threshold).
Binding materials for foundry sands will be rather changing by the evolutionary
and not the revolutionary way. More and more strong regulations concerning the
environment protection and growing social pressure are causing foundry plants to
either look for new, more friendly, technologies of molding and core sand prepara-
tion or try to improve and modify the already applied ones, to limit the emission of
harmful substances and unpleasant smells during preparations of sands, mold pour-
ing, cooling, and casting knocking out. These elements decide – to a significant
degree – on the foundry sector image. Simultaneously, this is forcing producers of
foundry materials to develop such binders which will meet these requirements. The
example of this trend can be molding sands with bentonite and substances generat-
ing lustrous carbon, substituting sea coal dusts [29–32].
Investigations concerning molding and core sands will be carried out in three
basic directions: the environment protection, technology (among others, work time
of sands, prolongation of sands storage time, higher dimensional accuracy of cast-
ings, castings quality improvement), and the production efficiency.
The market of molding sands was for many years dominated by sands with ben-
tonite (green sands) and sands with water glass hardened at the room temperature.
6
Table 1.2 Indicative exposure limit values applied in Poland and other countries for compounds emitted in casting process
WEL (Poland) TLV WELs (8) (G. Britan)
(4)
NDSCh TLV–STEL Long-term Short-term
NDS (8 h (30 min TLV–TWA(3) (15 min exposure limit exposure limit
reference reference (8 h reference reference (8 h reference (15 min reference
period) period) NDSP period) period) period) period) Comments
CAS mg/ mg/
Compounds number(5) mg/m3 ppm (7) m3 (6) ppm mg/m3 ppm m3 ppm mg/m3
Ammonia 7664-41- 14 28 25 18 35 25 25 18 35 25
7
Benzo(a)pyrene 50-32-8 0.002 – –
Benzene 71-43-21 1.6 1 3.25 1 3.25 Carc, Sk
Hydrogen cyanide 74-90-8 1 – 5 0.9 1 4.5 5 0.9 1 4.5 5 Sk
Diisocyanate 26,447- 0.03 0.09 –
methylene diphenyl – 40-5
mixed isomers
Toluene-2-6- 91-08-7 0.007 0.021 –
diisocyanate – mixed
isomers
Carbon disulfide 75-15-0 12.5 – – 5 15 5 15
Nitrogen dioxide 10,102- 0.7 1.5 – 0.5 0.96 1 1.91 0.5 0.96 1 1.91
44-0
Sulfur dioxide 7446-09- 1.3 2.7 0.5 1.3 1 2.7 0.5 1.3 1 2.7
5
Carbon dioxide 124-38-9 9000 27,000 – 5000 9150 1500 21,400 5000 9150 15,000 27,400
Ethylbenzene 100-41-4 200 400 – 100 441 125 552 100 441 125 552 Sk
Ethyltoluene 25,550- 100 – –
14-5
Phenol 108-95-2 7.8 16 – 2 7.8 4 6 2 7.8 4 16 Sk
1 Introduction
(continued)
Formaldehyde 50-00-1 0.37 0.74 – 2 2.5 2 2.5 2 2.5 2 2.5
Phosgene 75-44-5 0.08 0.16 – 0.02 0.08 0.06 0.25 0.02 0.08 0.06 0.25
2-Furaldehyde 98-01-1 10 25 2 8 5 20 2 8 5 20
1 Introduction
Glutaraldehyde 111-30-8 0.4 0.6 – 0.05 0.2 0.05 0.2 Sen

Cresol 95-48-7 22 – – 0.05 0.2 0.05 0.2 Sen
Xylene –o, −m, −p 95-47-6 100 – – 50 220 100 441 Sk
or mixed isomers BMGV
Adipic acid – 124-04-9 5 10 –
inhalable fraction
Methyl methacrylate 80-62-6 100 300 50 208 100 416
Methanol 67-56-1 100 300 200 266 250 333 200 266 250 333 Sk
Methylamine 74-89-5 5 15 –
Naphthalene 91-20-3 20 50 –
Methyl formate 107-31-3 100 200 – 50 125 100 210 100 250 150 375
Methyl acetate 179-20-9 179 1468 200 734 400 1468 200 734 40 1468
Tetraethyl 78-10-4 44 – – 5 44 5 44
orthosilicate
Hydrogen sulfide 7783-06- 7 14 – 30 35 200 232 5 7 10 14
4
Carbon monoxide 630-08-0 23 1217 20 25 100 117 20 23 100 117
Styrene 100-42-5 50 100 – 100 430 250 1080 100 430 250 1080
Toluene 108-88-3 100 200 50 191 100 384 Sk
Trimethylamine 75-50-3 12 24 –
Triethylamine 121-44-8 3 9 2 8 4 17 Sk
Sulfur trioxide 7446–11- 1 3 –
9
7
(continued)
8
Table 1.2 (continued)
WEL (Poland) TLV WELs (8) (G. Britan)

(4)
NDSCh TLV–STEL Long-term Short-term
NDS (8 h (30 min TLV–TWA(3) (15 min exposure limit exposure limit
reference reference (8 h reference reference (8 h reference (15 min reference
period) period) NDSP period) period) period) period) Comments
CAS mg/ mg/
Compounds number(5) mg/m3 ppm (7) m3 (6) ppm mg/m3 ppm m3 ppm mg/m3
Crystalline silica 14,808- 0.1

Quartz 60-7
Cristobalite – 14,464-
respirable fraction 46-1
Adapted from Refs. [26–28, 37]
Annotations
BMGVs Biological monitoring guidance values
Carc Capable of causing cancer and/or heritable genetic damage
Sen Capable of causing occupational asthma
Sk Can be absorbed through the skin. The assigned substances are those for which there are concerns that dermal absorption will lead to systemic toxicity
(1) Inhalable fraction: It is the fraction of total airborne particles that enters the body through the nose and/or mouth during breathing. This fraction correspond-
ing to particles with aerodynamic diameter (dae) ≤100 μm) is relevant to health effects anywhere in the respiratory tract such as rhinitis, nasal and lung cancer,
and systemic effects
(2) Respirable fraction dust: It is the fraction that penetrates to the deep lung where gas exchange takes place. The particle sizes of respirable dust are up to
10 microns
(3) TWA: Time-weighted average
(4) STEL: Short-term exposure limits
(5) CAS: Chemical Abstracts Service (Registry Number)
(6) mg/m3: milligrams/cubic meter of air
(7) ppm: parts per million (ml/m3)
(8) WELs: Workplace exposure limits (EU Directive 2009/161/EU)
1 Introduction
1 Introduction 9
Processes of sand binding by means of furan and phenol resins, hardened at a room
temperature, were developed in the 1950s of the twentieth century. At the end of the
1960s, the cold-box process for various resins was developed. The development of
sands with water glass, hardened by drying technique, started in the middle of the
1990s. Efforts are undertaken to use these sands, generally counted to sands with
inorganic binders (however, apart from water glass, these sands contain certain
organic additions for their properties improvement), as substitutes of widely applied
sands with organic binders. Molding sands with organic binders have several advan-
tageous features, which previous sands did not have. This concerns better efficiency,
higher reliability, and better mechanical properties. Foundry plants of aluminum
and copper alloys were the first plants in which sands with organic binders were
substituted by sands with water glass thermally hardened. The main reasons of
changing cores with organic binders (hot-box, warm-box, cold-box) for cores with
water glass constituted difficulties in removing these cores from the mold after cast-
ing (too low overheating degree in the case of aluminum alloys). In addition, sands
with water glass are considered to be environmental-friendly and not toxic.
Drawbacks of sands with water glass such as difficulty in knocking out, low
elasticity, or weak reclaimability can be improved by means of various additives or
modifiers (collagen, starch, dextrin). Several producers of foundry sand binders
developed their own technologies, based on water glass thermally hardened, of
trade names CORDIS®, AWB®, INOTEC®, and based on geopolymer of trade
name GEOPOL®. However, not every mold or core can be produced by this tech-
nology. It concerns especially large molds (of a few and a dozen or so tons) and
large cores.
At the development of new kinds of binders, the attention should be directed to
the following properties:
• Minimizing of binder additions.
• Low binder viscosity.
• Possibility of long-term storage of cores.
• Low level of unpleasant smells.
• Low emission during sand preparations and mold producing.
• Easy reclamation of spent sands.
• Low level or a lack of nitrogen in a binder, especially when sands are used for
cast steel castings.
• Low level of sulfur in a binder, when sands are used for spheroidal cast iron
castings.
According to the assumed rule, the best way of reduction of contaminations is
their elimination at a source. In the case of foundries, the most efficient method of
VOC reduction is the substitution of traditional binders – based on petroleum indus-
try products – by less harmful binders based either on inorganic polymers (e.g.,
geopolymers) or on natural polymers. In order to satisfy this task, the hybrid binder
consisting of alkaline silicate with the addition of, e.g., hydrolyzed collagen was
developed. This new binder – of a low VOC emission – allowed to decrease signifi-
cantly amounts of VOC released every year by the foundry industry [33–35].
10 1 Introduction
The evaluation of harmfulness of sands applied for molds and cores contains two
basic elements:
• Emissivity of harmful gases and dusts during such operations as preparations of
sands, their molding, making cores, mold pouring with liquid metal, mold cool-
ing, casting knocking out, and spent sand reclamation.
• Possibility of the elution of dangerous substances from spent sands into the envi-
ronment during these sands’ storage or functional utilization. Molding sands
with binders, from which harmful substances are not eluted, can be utilized in
other fields, due to which their storage is avoided [36].
Therefore, at the evaluation of the given sand influence on the environment, these
two problems should be also taken into account. Only when such investigations
were performed the total evaluation of the given sand harmfulness would be
achieved.
References
1. Holtzer M (2018) Adjusting the foundry plants operations to the sustainable development
strategy – the success condition. Foundry J Polish Foundrymen’s Assoc 68:20–21
2. Patange GS, Khond MP, Chaudhari NV (2012) Some studies and investigations of foundry
wastes for sustainable development. Int J Ind Eng Res Dev 3:51–57
3. Wadhwa R (2015) Sustainable manufacturing in SMEs: Technology options. Int J Comput Sci
Issues 12:107–112
4. Guangkuo A (2014) The establishment of sustainable development capacity of the foundry
industry index evaluation system. 71st World Foundry Congr. Bilbao, Spain, p 19–21
5. Engelhardt T (2010) New concepts to reduce the emission from green sand. Fonderie Magazine
(7) : 24−36
6. Garbarz B (2008) Advances in iron and steel technologies meeting the principles of sustainable
development. Pr Inst Metal Żelaza 60:1–7. (in Polish)
7. Census of World Casting Production (2018) Mod Cast 2019 December 24–5
8. Elliehausen HJ, Knecht U, Maa β-Rühl B (1984) Schdstofbelastung durch formsande einer
Eisengieβerei. Gentner Verlag, Stuttgart
9. Palmer WG, Scoott WD (1981) Lung cancer in ferrous foundry workers: a review. Amer Ind
Hyg Assn J 42:329–340
10. LaFay VS, Neltner S, Carroll D, Couture DJ (2010) Know the environmental impact of your
additives. Mod Cast 10:27–29
11. Regulation (EC) no 1907/2006 of the european parliament and of the council of 18

december 2006 concerning the Registration, Evaluation, Authorisation and Restriction of
Chemicals (REACH)
12. Crandell GR, Schifo J, Mosher G (2006) CERP Organic HAP emission measurements for
iron foundries and their use in development of an AFS HAP guidance document. Trans Am
Foundry Soc 114:1–17
13. Kumar R, Abhishek MK, Fuller A, Bosco M, Rego JV (2017) Study on mechanical properties
of bio based and inorganic binders for the preparation of core in metal casting Energy and
Power. 7:136–141
14. Glowacki CR, Crandell GR, Cannon FS, Voi RC, Clobes JK, Furness JC et al (2003) Emissions
studies at a test foundry using an advanced oxidation-clear water system. Am Foundry Soc
Trans 3:22
1 Introduction 11
15. Wang Y, Cannon FS, Salama M, Goudzwaard J, Furness JC (2007) Characterization of hydro-
carbon emissions from green sand foundry core binders by analytical pyrolysis. Environ Sci
Technol 41:7922–7927
16. Technikon L (2000) US Army Task N256 Ashland Core Binder Replacement
17. ASK Chemicals (2016) Newest technology platform for cold box binders. Foundry Trade J
190:240–242
18. Riberio MG, Filho WR (2006) Risk assessment of chemicals in foundries: the International
Chemical Toolkit pilot-project. J Hazard Mater 136:432–437
19. Humfrey CDN, Levy LS, Faux SP (1996) Potential carcinogenicity of foundry fumes: a com-
parative in vivo-in vitro study. Food Chem Toxicol 34:1103–1111
20. Scarbel P, Bats CE, Griffin J (2006) Effect of mold and binder formulation on gas evolution
when pouring aluminum casting. AFS Trans 114:435–445
21. Bobrowski A, Holtzer M (2009) Assessment of environmental influence of bentonite and lus-
trous carbon carrier – in an ascpect of gases emission. Arch Foundry Eng 9:21–24
22. Teles MT, Delerue-Matos C, Alvim-Ferraz M (2005) Determination of free furfuryl alcohol in
foundry resin by chromatographic techniques. Anal Chim Acta 537:47–51
23. Kubecki M, Holtzer M, Grabowska B, Bobrowski A (2011) Development of method for iden-
tification of compounds emitted during thermal degradation of binders used in foundry. Arch
Foundry Eng 11:125–130
24. Ji S, Wan L, Fan Z (2001) The toxic compounds and leaching characteristics of spent foundry
sands. Water Air Soil Pollut 132:347–364
25. Gromiec JP, Czerniak S (2002) Polish and worldwide criteria for assessing exposure to chemi-
cals: procedures and applications. Occup Med (Chic Ill) 53:53–59
26. Directive (EU) 2017/164 - indicative occupational exposure limit values
27. Directive (EU) 2017/2398 on the protection of workers from the risks related to exposure to
carcinogens or mutagens at work
28. Regulation of the Minister of Family, Labour and Social Policy of June 12-th 2018, concerning
the highest allowable concentrations and intensities of harmful for health factors in the work
environment 2 Dz. U. 2018, item 128 (in Polish)
29. Holtzer M, Dańko J, Dańko R (2007) Possibilities of formation of dioxins and furans in metal-
lurgical processes as well as methods of their reduction. Metalurgija 46:285–290
30. Holtzer M (2003) Directions of development of molding and core sand with organic binders.
Arch Foundry Eng 3:189–196
31. Wolff T, Steinhaeuser T (2004) AWB – an environment friendly core production technology.
Giesserei 91:80–84
32. Howden JD (2014) Green sand “less is best” a more sustanable philosophy for change.
Proceed. Mater. 71st World Foundry Congr., Bilbao, Spain, pp 19–21
33. Wang J, Fan Z, Wang H (2007) An improved sodium silicate binder modified by ultra-fine
powder materials. China Foundry 4:26–30
34. Fan G, Gu Z, Yang L, Li F (2009) Nanocrystalline zinc ferrite photocatalysts formed using the
colloid mill and hydrothermal technique. Chem Eng J 155:534–541
35. Kmita A, Drożyński D, Roczniak A, Gajewska M, Marciszko M, Górecki K et al (2018)
Adhesive hybrid nanocomposites for potential applications in molding sands technology.
Compos Part B Eng 146:124–131
36. Holtzer M, Dańko R, Kmita A (2016) Influence of a reclaimed sand addition to molding sand
with furan resin on its impact on the environment. Water Air Soil Pollut 227:1–12
37. EH40/2005 (2018) Workplace exposure limits. Third edition, published in 2018 by The
Stationary Office
38. Holtzer M, Danko J, Danko R (2007) Possibilities of formation of dioxins and furans in metal-
39. Lv P, Zheng M, Liu G, Liu W, Xiao K (2011) Estimation and characterization of PCDD/Fs and
dioxin-like PCBs from Chinese iron foundries. Chemosphere 82:759–763
12 1 Introduction
40. Grochowalski A, Lassen C, Holtzer M, Sadowski M, Hudyma T (2007) Determination of

PCDDs, PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland. Environ
Sci Pollut Res 14:326–332
41. Suhr M, Klein G, Kourti I, Gonzalo MR, Santonja GG, Roudier S, et al. (2015) Best Available
Techniques (BAT) Reference Document for the Production of Pulp, Paper and Board
Part I
Organic Chemistry
Chapter 2
General Principles of Organic Chemistry
2.1 Organic Compounds: Structure and Bonding
Structure of Organic Compounds

Organic chemistry is the chemistry of carbon compounds. Carbon is the basic com-
ponent of organic compounds, but a majority of these compounds contain also
hydrogen, nitrogen, oxygen, sulfur, phosphorus, chlorine, or other elements.
Carbon, as the element of group IV, can share four valence electrons and form four
strong atomic bonds. In addition, carbon atoms can join with each other forming
long chains and rings [1].
Atoms can join into molecules, since particles are more stable (has lower energy)
than individual atoms of which they were formed. Therefore, when the chemical
bond is formed, the energy is always released from the system. However, when the
chemical bond decomposes, the energy must be supplied to the system. Chemical
bonds can have different characters.
The organic compound structure consists of a hydrocarbon core (chain or ring)
or of a chain or ring with built-in heteroatoms, constituting the particle backbone
and linked with this backbone substituents and functional groups [2–4].
Substituent is an atom or a group of atoms with which the hydrogen atom was
substituted in a chain or ring.
Functional group is an atom or a group of atoms linked with the parent structure.
Functional groups decide on the chemical properties of organic compounds (there-
fore multiple bonds are considered to be functional groups). One, two, three, or
more functional groups can occur in an organic compound. Since the distinction
between two notions, substituent and functional groups, is difficult, it can be
assumed that – from the point of view of the chemical reaction – substituents are
atoms or groups of atoms not taking part in the given reaction, while functional
groups are those which are taking part in the reaction.
Types of Bonds in Organic Compounds
Ionic Bonds

16 2 General Principles of Organic Chemistry
Presence of eight electrons in the outer shell (i.e., noble gas structure) provides
especially stable structure of the element. Several elements of the main group of the
periodic table are striving to obtain such structure either by giving electrons (form-
ing cations) or by taking electrons (forming anions). Ions formed in this way are
joining with each other, due to the electrostatic attraction, forming compounds of
A+B− type; this is an ionic bond.
Atomic Bonds
Not all elements, including also carbon, are able to form ionic bonds. It results
from the fact that atoms of such elements require too much energy for giving or tak-
ing electrons, in order to achieve the noble gas configuration. As an example, carbon
has the electronic configuration 1s22s22p2, which means that in order to obtain the
stable noble gas configuration, it must give or take four electrons, achieving either
the helium (He 1s2) or neon (Ne 1s22s22p6) structure. Therefore carbon is joining
with other elements by common electron pairs forming single, double, and triple
bonds. Such bonds are called atomic bonds (covalent bonds). This is a symmetric
bond because two binding electrons are equally used by two equal carbon atoms.
A majority of chemical bonds are neither fully ionic nor fully atomic since bind-
ing electrons are more attracted in the direction of one of the atoms (more electro-
negative), forming the polarized atomic bond [5].
2.2 Organic Chemical Reactions: Classifying
Classifying in Respect of Structural Changes

There are four general types of organic reactions, which involve structural changes
in substrates [1].
Addition reaction – two substrates are joined together forming one new product.
Substitution reaction – substrates are exchanging fragments of their particles form-
ing new products.
Elimination reaction – single substrate disintegrates into two products.
Rearrangement reaction – in a single substrate, the rearrangement of bonds occurs.
Classifying in Respect of the Reaction Type
Oxidation and Reduction Reactions
Carbon atoms have various oxidation degrees, from −4 (e.g., CH4) to +4 (e.g.,
CO2), depending on substituents. The oxidation in inorganic chemistry is defined as
a loss of one or more electrons by the given atom while the reduction as obtaining
of one or more electrons. The problem whether the given carbon atom was reduced
or oxidized during the reaction is determined in organic chemistry by the change of
the number of C–H bonds and the change of bonds of carbon with more electro-
negative elements (N, O, F, Cl, Br, I, S). Bonds between carbon atoms are omitted.
Such calculation should be performed for each carbon atom, which is changing
during the reaction.
2.2 Organic Chemical Reactions: Classifying 17
Table 2.1 Classification of organic compounds on the bases of functional groups

Class of chemical Group name in
compound Functional group Prefix Suffix
Carboxylic acid Carboxyl-
Sulfonic acid Sulfo-
Ester R-Oxycarbonyl- -an R
Nitrile Cyano- -nitrile
Alcohol −O − H Hydroksy-

Phenol
Ether Ether
Amine C − NH2 -amine

Alkenes −C = C−
Alkynes −C ≡ C−
Alkanes −C − C−
−CH2OH− Methylol group
CH3− Methyl group
CH3O− Methoxy group
C6H5O− Phenoxy group
−CH2− Methylene group
Aldehyde −C = O Carbonyl group
Ketone
Adapted from Refs. [2, 6]
• When the number of C–H bonds increases and/or the number of bonds of carbon
with more electronegative elements decreases, it means that such carbon atom
was reduced (i.e., it is on a lower oxidation degree).
• When the number of C–H bonds decreases and/or the number of bonds of carbon
with more electronegative elements increases, it means that such carbon atom
was oxidized (i.e., it is on a higher oxidation degree).
Classifying Based on Functional Groups

Organic compounds can be grouped, taking into account their structural features
and related to them similar physical and chemical properties. Compounds included
into the given group are characterized by functional groups (Table 2.1). Functional
groups are the sites of chemical reactions in organic compounds.
2.3 Hydrocarbons
Hydrocarbons are compounds which contain only carbon and hydrogen. Atoms can
be joined together by single, double, or triple bonds in chains of an arbitrary length
or in rings of various sizes. Hydrocarbons are divided into aliphatic (chain), cyclic,
and aromatic hydrocarbons. Among aliphatic and cyclic hydrocarbons, there are
saturated hydrocarbons, i.e., alkanes or cycloalkanes, and unsaturated hydrocar-
bons. Unsaturated hydrocarbons contain alkenes (with double joints), alkynes (with
triple joints), and alkadienes (with two double joints) as well as cycloalkenes,
cycloalkynes, and cycloalkadienes, respectively (Fig. 2.1). Carbon obtains +4
valence in organic compounds.
The selected substances from individual hydrocarbon groups are shown in
Table 2.2.
2.3.1 Alkanes
Alkanes contain saturated hydrocarbons in which carbon atoms are joined with each
other by single bonds only.
According to the binding systematic of IUPAC1 [7], chains of carbon atoms in
particles of alkanes can be both normal and branched, but cannot form closed loops.
The general molecular formula of alkanes is of a form: CnH2n + 2. The alkanes group,
put in order according to the carbon chain length, constitutes the alkanes homolo-
gous series. This series is as follows (all names of alkanes have at the end -ane)
(Table 2.3) [6].
The first four saturated hydrocarbons of the homologous series are gases. Alkanes
having from 5 to 15 carbon atoms in a particle are liquids, while the ones in which
the number of carbon atoms exceeds 15 are solids.
Natural sources of saturated hydrocarbons are natural gas, crude oil, fossil wax,
and paraffin. Natural gas is a mixture of gaseous hydrocarbons. Its main component
is methane (50–98%) and then ethane, propane, and butane. Crude oil contains
alkanes (30–80%) and various amounts of cycloalkanes and aromatic hydrocarbons.
IUPAC – International Union of Pure and Applied Chemistry.

1
2.3 Hydrocarbons 19
Fig. 2.1 Schematic division of hydrocarbons
Alkanes can be obtained by the thermal decomposition of carboxylic acid salts.

For example, methane is obtained by heating sodium acetate (Eq. 2.1):
hν
CH 3 COONa + NaOH → CH 4 + Na 2 CO3 (2.1)

Saturated hydrocarbons can be also obtained by catalytic hydrogenation of
unsaturated hydrocarbons or by electrolysis of carboxylic acid salts.
Alkanes are highly hydrophobic, do not mix with water, are not wetted by water,
and are not soluble in water. However, they easily dissolve in nonpolar, weakly
polar, and moderately polar organic solvents. These substances are easily flamma-
ble. Gaseous hydrocarbons form explosive mixtures with the air. Alkanes are weakly
reactive, but under certain conditions can violently react, e.g., in a substitution reac-
tion, when the hydrogen atom is substituted by another atom, the most often by
halogen (X) (Eqs. 2.2 and 2.3):
hν
R − H + X 2 → R − X + HX (2.2)
Bromination:
HC ≡ CH + Br2 → CHBr = CHBr

(2.3)
ethine 1, 2 dibromoethene
CHBr = CHBr + Br2 → CHBr2− CHBr2
1, 2 dibromoethene 1,1, 2, 2 tetrabromoethane
Reactions of alkanes with oxygen:

20
Table 2.2 Simplified formulas, names, and symbols of abbreviations of the selected hydrocarbon groups
Alkyl groups of aliphatic hydrocarbons
Hydrocarbon Simplified formula Group name
Methane CH3 Methyl group, (Me)
CH4 CH2 Methylene group
Methyne group
Ethane CH3CH2 Ethyl group, (Et)
CH3CH3 CH3CH Ethyl group
CH3C Ethylidyne group
CH2CH2 Ethylene group
Propane CH2CH2CH3 Propylene group, (Pr)

CH3CH2CH3
CH3CHCH3 Isopropyl group, (i-propyl)
Alkyl groups of unsaturated aliphatic hydrocarbons

Hydrocarbon Simplified pattern group Name of group
CH2 H2C CH Ethyl, vinyl
EtheneH2C
CH CH2 H3C CH CH Propenyl
PropeneH3C
CH2 CH CH2 Prop-2en-1-yl
Isopropenyl, 1-methylvinyl
H3C C CH2
2 General Principles of Organic Chemistry
CH2 H3C CH2 CH CH2 But-1en-yl
ButeneH3C CH2 CH
CH3 CH CH CH3 CH3CH CH CH2 But-2-en-1-yl
2-Butene
CH HC C Ethyne
EthyneHC
Propen-2-en-1
2.3 Hydrocarbons
PropyneH3C
C CH CH2 C CH
Aryl groups of aromatic hydrocarbons
Hydrocarbon Simplified pattern group Name of group
Phenyl
Benzene
o-, m-, p-phenyl
α-Naphthyl (C10H7-)
8 1
7 2
6 3
4 β-Naphthyl (C10H7-)
Naphthalene 5
21
(Continued)
Table 2.2 (Continued) 22
CH3 Benzyl group

CH2
Benzylidene group
HC
Toluene
Benzylidene group
C
α-Phenyl (C6H5-phenyl group)

1 2
CH2CH3 CH CH3
β-Phenyl (C6H5-phenyl group

CH2 CH2
Ethylbenzene
Styrene
CH CH2 CH CH2
Styrene
Adapted from Adapted from Ref. [2]
2.3 Hydrocarbons 23
Table 2.3 The alkanes homologous series

Methane CH4 Hexane C6H14
Ethane C2H6 Heptane C7H16
Propane C3H8 Octane C8H18
Butane C4H10 Nonane C9H20
Pentane C5H12 Decane C10H22
Methane CH4
Ethane CH3–CH3
Propane CH3–CH2–CH3
Butane CH3–CH2–CH2–CH3
• Complete burning (Eq. 2.4):
CH 4 + 2O2 → CO2 + 2H 2 O + 890 kJ / mol (2.4)
• Semi-burning (Eq. 2.5):
2CH 4 + 3O2 → 2CO + 4H 2 O (2.5)

Under the influence of high temperatures, alkanes are decomposing.
Alkanes, in a similar fashion as other hydrocarbons, indicate the isomeric effect.
In this case it is the chain isomer, being various chain designs of isomeric particles.
Isomerism – the effect of an occurrence of two or more compounds of the same
molecular formula, but of various molecular structures, e.g.,
H H H H H
H H C HH
H C C C C H
H C C C H
H H H H
H H H
n-butane 2-methylpropane
C4H10 Isobutane
C4H10
2.3.2 Alkenes
General formula of alkenes is CnH2n, where n means the number of carbon atoms in
a chain. Alkenes have the double bond between carbon atoms (C=C). This bond
cracks during the addition reaction. Due to the fact that alkenes have double bond in
their chain, they are unsaturated hydrocarbons. They decolor bromine water in the
addition reaction.
CH2 = CH2 CH2 = CH − CH3
ethene propene
CH2 = CH − CH2 − CH3 CH2 = CH − CH2 − CH2 − CH3
butene pentene
Table 2.4 The homologous C2H4 ethene C7H14 heptene

series of alkenes
C3H6 propene C8H16 octene
C4H8 butene C9H18 nonene
C5H10pentene C10H20 decene
C6H12 hexene
Names of alkenes are formed from the appropriate alkanes names by changes of
their endings (−ane turns into -ene). The homologous series of alkenes is as follows
(Table 2.4):
In the case of unsaturated hydrocarbons occurs the isomerism, related to the
double bond placement in the carbon chain, i.e., the so-called double bond isomer-
ism (Eq. 2.6):
1 2 3 4
CH 2 = CH − CH 2 − CH 3 but
1 en
(2.6)
1 2 3 4
CH 3 − CH = CH − CH 3 but 2 en

and geometric isomerism (Eq. 2.7):
H H H CH3
C C C C
H3C CH3 H3C H
cis-but-2-ene trans-but-2-ene (2.7)

The compound having substituents at the same side of the double bond is called
cis-, while the isomer with substituents at the reverse side is called trans- (trans
compounds are more stable).
Alkenes containing 1 to 4 carbon atoms in their chain are gases, containing from
5 to 18 carbon atoms are liquids, while those having at least 18 carbon atoms are
solids. Alkenes are obtained on the industrial scale by cracking of light petrol. They
can be obtained in the laboratory, e.g., by dehydration of ethyl alcohol (Eq. 2.8):
CH 3 − CH 2 − OH → CH 2 = CH 2 + H 2 O
(2.8)
ethyl alcohol ethene
2.3 Hydrocarbons 25
Alkenes are highly reactive, which is caused by the double bond presence. These
substances easily react in:
• Addition reaction of, e.g., hydrogen (Eq. 2.9):
CH 2 = CH 2 + H 2 = CH 3 − CH 3
(2.9)
ethene ethane
• Polymerization reaction (Eq. 2.10):
n CH 3 = CH − CH 3 → ( −CH − CH − CH 3 − )n
(2.10)
propene
• Burning reaction of ethene (Eqs. 2.11 and 2.12):
C2 H 4 + 3O2 = 2CO2 + 2H 2 O complete burning (2.11)
C2 H 4 + 2O2 = 2CO + 2H 2 O non complete burning (2.12)
2.3.3 Alkynes
The general molecular formula for alkynes is CnH2n−2, where n means the carbon
atoms number in a chain. Alkynes analogically as alkenes are unsaturated hydrocar-
bons, which means that they are also easily taking part in the addition reaction.
Since they have the triple bond (−C ≡ C−), they are more reactive than alkanes and
alkenes. They are unstable and subjected to several natural processes. Their names
are formed by changing the ends and adding the number of the carbon atom at
which the triple bond occurs (Table 2.5).
Ethine, i.e., acetylene, can be obtained:
• By hydrolysis of calcium carbide (Eq. 2.13):
CaC2 + 2HOH → HC ≡ CH + Ca ( OH )2 (2.13)

• By pyrolysis of light hydrocarbons, mainly methane (this is highly endothermic
reaction) (Eq. 2.14):
1500° C
2CH 4 → HC ≡ CH + 3H 2 + 377 kJ (2.14)
Alkynes are not water soluble and undergo reactions:

• Addition of hydrogen, halogen, or water:
Partial hydrogenation (Eq. 2.15):
Table 2.5 The homologous series of alkynes
26
H C C H H H
C2H2 ethine H C C C C H
H H
C4H6 1-butyne
H H H H
H C C C H H C C C C C H
H H H H
C3H4 propyne C5H8 1-pentyne

2.3 Hydrocarbons 27
H2
HC ≡ CH → H 2 C = CH 2 (2.15)
ethine catalyst ethene
Complete hydrogenation (Eq. 2.16):
H2
H 2 C = CH 2 → CH 3 − CH 3 (2.16)
ethene catalyst ethane
• Polymerization (Eq. 2.17):
n CH ≡ CH → ( −CH = CH − )n
(2.17)
ethine
2.3.4 Cycloalkanes
Hydrocarbon chains can create rings forming cyclic substances. Cycloalkanes are
saturated hydrocarbons, which particles contain either one or more non-substituted
rings or rings connected with side chains of saturated hydrocarbons. Cycloalkanes
contain repeatable elements: – CH2 –, which means that their molecular formula can
be presented as CnH2n.
The simplest, single-ring cycloalkanes form the homologous series of com-
pounds of an increasing ring size. Their names are formed from names of appropri-
ate alkanes, with added prefix cyclo- (Table 2.6).
Cycloalkanes can be obtained, among others, by hydrogenation of aromatic
hydrocarbons (high pressure, increased temperature, catalyst: Ni) (Eq. 2.18):
cat.
+ H2
2.5 MPa
200°C
(2.18)
benzene (C6H6) cyclohexane (C6H12)

or by cyclization (closing of ring) of two substituted chain compounds (Eq. 2.19):
CH2 Cl CH2
Zn, Na+
H2C H2C
CH2 Cl CH2
+ 2HCl (2.19)
1,3 – dichloropropane cyclopropane
Table 2.6 The homologous series of cycloalkanes

Compound Chemical formula Structural formula
Cyclopropane C3H6 CH2
H2 C CH2
Cyclobutane C4H8 H2 C CH2
H2 C CH2
Cyclopentane C5H10 H2C CH2
H2C CH2
CH2
Cyclohexane C6H12 H 2C CH2
H 2C CH2
H 2C CH2
Cycloalkanes are hydrophobic, form explosive mixtures with the air, and are eas-
ily volatile.
In respect of chemistry, simple cycloalkanes containing five or more carbon
atoms in a ring are similar to alkanes:
• They are oxidizing.
• They react with chlorine and bromine (Eq. 2.20):
– Cl
+ Cl2 hv
+ HCl
cyclopropane chlorocyclopropane (2.20)
C3H6 C3H5Cl

• They are dehydrogenizing (aromatized) (catalyst: Pt, 500 °C) (Eq. 2.21):
2.3 Hydrocarbons 29
-3 H2
(2.21)
C6H12 cyclohexane C6H6 benzene
Cycloalkanes are applied as solvents and in chemical syntheses.
2.3.5 Cycloalkenes
Cycloalkenes are built of rings containing one double bond C=C (Table 2.7). The
general formula of cycloalkenes is CnH2n−2.
They are liquids insoluble in water. Their chemical properties are similar to the
ones of alkenes. Since they are unsaturated compounds, they are taking part in addi-
tion reactions (Eq. 2.22):
Br
+ Br2
Br (2.22)
cyclohexane 1,2-dibromocyclohexane
Table 2.7 The homologous Compound Chemical formula Structural formula

series of cycloalkenes CH2
Cyclopropene C3H4
HC CH
Cyclobutene C4H6 H2C CH2
HC CH
Cyclopentene C5H8 HC CH
H2C CH2
CH2
Cyclohexene C6H10 HC CH
H2C CH2
H2C CH2
These compounds are used as solvents and in organic syntheses.
2.3.6 Aromatization and Benzene
Aromatic hydrocarbons have chains closed into rings. In between carbon atoms, the
single and double bonds alternately occur. It means that they are quasi-unsaturated
compounds. In contrast with alkenes, arenes can have a few double bonds. A special
structure of these hydrocarbons causes that they do not always behave as saturated
compounds, neither do they have an unsaturated character. Their bond structure
causes that they are very stable and their reactivity is significantly different than the
reactivity of other unsaturated hydrocarbons [3]. The simplest arene is benzene,
which molecule can be presented as follows (Kekule’s formula) (Eq. 2.23):
H
H C H
C C
C C
H C H (2.23)
H
Many aromatic compounds have both common and IUPAC names. These com-
mon names are shown below their UPAC names (Eq. 2.24):
CH CH2 OH H3C CH3
vinylbenzene benzol isopropylbenzene (2.24)

(styrene) (phenol) (cumene)
(however such form is not used in the case of successive aromatic hydrocarbons).
Benzene homologues are organic compounds containing benzene ring and one
or a few saturated hydrocarbon chains, e.g. (Eq. 2.25),
2.3 Hydrocarbons 31
CH3 C2H5
benzene methylbenzene ethylbenzene

(toluene)
(2.25)

C6 H6 C6 H5 − CH3 C6 H5 − CH2 − CH3
Xylenes o-, m-, and p- are isomers, differing by mutual positions of methylene
groups (Eq. 2.26):

CH3 CH3
CH3
1
1 CH3 1 2
2 2 6
6 6
5
5 5 3
3 4
3 CH3 4
4
CH3
1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene (2.26)

o-xylene m-xylene p-xylene
Structural isomers are presented below (Eq. 2.27): 2-methylphenol (o-cresol),
3-methylphenol (m-cresol), and 4-methylphenol (p-cresol). They have similar
chemical properties, but differ slightly in melting and boiling points:

OH OH OH OH
CH3
CH3
CH3
benzol o-cresol m-cresol p-cresol (2.27)
(phenol) (2-methylphenol) (3-methylphenol) (4-methylphenol)
Some compounds, which apart from carbon atoms, have in their rings atoms of
other elements can have aromatic character (aromatic heterocyclic compounds)
(Eq. 2.28):
H2SO4 NO2
+ HNO3 + H2O nitration
H2SO4 SO3H
+ SO3
+ H2O sulfonation
FeCl3 Cl
+ Cl2
+ HCl chlorination
AlCl3 CH3
+ CH3Cl
+ HCl alkylation
AlCl3 COCH3
+ CH3COCl + HCl acylation
Fig. 2.2 The characteristic reaction of aromatic hydrocarbons

..
N
.. ..
N O
.. N N
.. N
.. ..
H (2.28)
pyrrole furan pyridine pyrimidine quinoline
Benzene and the basic aromatic compounds are obtained, in large amounts, from
the crude oil distillation, from gas pitch (obtained during the coal carbonization2),
and from ethyne (acetylene) (Eq. 2.29):
2
Hard coal is a mixture composed mainly of the network of, similar to benzene, rings connected
with each other. When coal is heated to a temperature of 1000 °C without the air access, the ther-
mal decomposition occurs and the mixture of compounds, possible to be distilled – known as gas
pitch – is obtained.
2.3 Hydrocarbons 33
Fig. 2.3 Oxidation of CH3 COOH

aromatic hydrocarbons oxidation
toluene benzoic acid
CH3 COOH
oxidation
CH3 COOH
o-xylene orthophthalic acid
CH
HC CH
500 °C
HC CH
CH
(2.29)
acetylene (ethine) benzene
Aromatic hydrocarbons are liquids or solids, not water soluble. Hydrocarbons

containing more than one aromatic ring are usually solids, often of a high boiling
point and melting temperature. A large group of these compounds is cancerous or
mutagenic.
Aromatic hydrocarbons are applied in production of high-octane petrol, solvents,
chemical compounds, and medicines as well as in organic syntheses.
Electrophilic Substitution
The bond structure in arenes cause that they are very stable, and the ring reactivity
is relatively low. The characteristic reaction of aromatic hydrocarbons is the electro-
philic substitution in the aromatic ring (Fig. 2.2):
In alkyl derivatives of benzene, there are aliphatic (side chains) and aromatic
fragments (rings). Reactions can occur in both parts of a particle. However in prac-
tice, reactions of electrophilic substitution in benzene alkyl derivatives and in other
aromatic hydrocarbons occur always only in rings.
Oxidation of Aromatic Hydrocarbons
At first, side chains will be oxidized without disturbing the aromatic system. It is
possible to obtain benzoic acid from toluene and dicarboxylic acids from xylene
(Fig. 2.3).
Table 2.8 Physical properties and structures of aromatic hydrocarbons from BTEX group
34
Molecular mass [g/ Density at 20 °C [g/ Melting point

Compound Structural formula Chemical formula mol] cm3] [oC] Boiling point [oC]
Benzene C6H6 78.11 0.874 5.5 80
Toluene C6H5CH3 92.14 0.873 −95 110.6
Ethylbenzene C6H5C2H5 106.17 0.867 −95 136.2
o-Xylene C6H4(CH3)2 106.17 0.880 −25 144
m-Xylene C6H4(CH3)2 106.17 0.861 −48 138
p-Xylene C6H4(CH3)2 106.17 0.861 13 138.3

2.3 Hydrocarbons 35
2.3.6.1 Aromatic Hydrocarbons from BTEX Group
Out of aromatic hydrocarbons, two groups of substances, which usually occur in the
casting production – mainly in molding sands with bentonite and with additions
containing carbon or in chemically bound molding sands – will be discussed.
BTEX is an acronym, related to the small group of aromatic hydrocarbons: ben-
zene, toluene, ethylbenzene, and xylene (Table 2.8). These are the so-called volatile
organic compounds (VOCs)3 . They are obtained from the crude oil treatment and
are applied mainly as solvents. All these substances are harmful for health and can
negatively influence the central nervous system. .
Benzene (carcinogenicity 1A can cause cancer, while mutagenicity 1B can cause
genetic disorders) is a volatile, colorless, flammable liquid. It enters organisms by
airways, but can be also – to a limited degree – absorbed by the skin and from the
alimentary canal. It is a dangerous substance due to its flammability as well as toxic-
ity (inhaling benzene causes pathological blood changes, which can lead to leuke-
mia [8]). Benzene toxic influences cause narcotic effects in the central nervous
system. Benzene poisoning, in its initial phase, causes sensitization of mucous
membranes of airways and eyes. However, the strongest symptoms are the result of
benzene influencing the central nervous system. Other symptoms of chronic ben-
zene poisoning are disturbances of the alimentary canal and hematopoietic necrosis
(lack of appetite, headaches, drowsiness, excitability).
Toluene (carcinogenicity 3 – toxic for reproduction) is a colorless liquid of a
characteristic smell, twice less volatile than benzene. Toluene is absorbed by air-
ways and in a liquid state also by the skin. Its toxic influence is similar to the ben-
zene influence. However, toluene influences more strongly the nervous system and
significantly weaker the hematopoietic system. It causes different changes than ben-
zene, e.g., it does not cause leukemia. Acute poisonings by toluene can cause head-
aches, imbalances, nausea, vomiting, and loss of consciousness. Chronic poisonings
are manifested by mucous membrane irritations, throat inflammation, and dizziness.
Ethylbenzene is mainly absorbed by airways. It irritates mucous membranes of
the eyes, nose, and airways. At high concentrations it can influence the central ner-
vous system. Dizziness and loss of consciousness can sometimes occur. A long
contact with the skin can cause its inflammation and/or allergic effects.
Xylenes (o-xylene, m-xylene, p-xylene) are colorless liquids, flammable, and
harmful for the human organisms. Xylenes are absorbed by the respiratory system,
from the intestinal tract and through a skin. They have irritating and depressive
effects on the central nervous system. At high concentrations they have narcotic
effects causing cardiac rhythm disturbances, loss of consciousness, and death. At a
lower poisoning level, the person is tired, is dizzy, and has difficulty breathing.
Substance vapors irritate mucous membranes of the eyes and throat. Disturbances
of the digestive tract such as loss of appetite, vomiting, and diarrhea also occur.
3
According to the Directive 2004/42/EC (Paints Directive) [28], the name volatile organic com-
pound (VOC) means any organic compound of the boiling temperature lower than, or equal,
250 °C, measured under the standard pressure, being 101.3 kPa.
2.3.6.2 Polycyclic Aromatic Hydrocarbons (PAHs)
The numerous groups of aromatic hydrocarbons contain condensed systems of ben-

zene rings.
Among them, the numerous and dangerous group constitute polycyclic aromatic
hydrocarbons (PAHs) of a ring structure characterized by similar physical–chemical
properties [9]. PAHs – in a pure state – occur as colorless, white, bright yellow, or
bright green crystals. These substances are slightly soluble in water, while much
better soluble in organic solvents. More than 100 various PAHs are known. The
most often 17 PAHs occur in the environment. Their physical–chemical properties
are presented in Table 2.9. PAHs are mainly formed in pyrolysis of organic sub-
stances occurring in several industrial processes and also under conditions of not
complete burnings (e.g., forest fires, waste incineration, car exhausts, cigarette
fumes). A majority of PAHs occur as vapors or aerosols in the air. PAHs from the air
are depositing on dust particles of equivalent grain diameters, being approximately
0.5 nm, and together with them are falling down on soils, vegetables, and surface
waters. PAH substances of a lower molar mass have certain volatility, while sub-
stances of a higher molar mass are solids. These substances do not occur as indi-
vidual ones but always as mixtures. When in the environmental test one substance
from this group is found, it means that other PAH substances are also present. PAH
substances occur in all elements of the human environment: in the air, water, soil,
and food. Thus, the exposure to their influence is universal. They can reach the
human body during eating, by inhaling, and through a skin. At the occupational
exposure, the main way of absorbing PAHs is the respiratory system into which less
volatile substances, including benzo(a)pyrene, enter as aerosols adsorbed on dust
particles (most often respirable). At the environmental exposure, the main way of
absorbing PAHs is the gastrointestinal tract. These substances as the air contami-
nants arouse more and more interests since some of them are highly carcinogenic or
mutagenic (Table 2.9). The most dangerous substance from the PAH group is
benzo(a)pyrene, since it is widespread and highly carcinogenic.
2.4 Hydrocarbons with Functional Groups
2.4.1 Alcohols and Phenols
Alcohols are organic compounds in which molecules of one or more hydrogen

atoms are substituted by hydroxyl functional group –OH. This –OH group can be
connected either to carbon from the aliphatic chain in the hybridization degree sp3
(aliphatic alcohols) or to carbon from the side aliphatic chain in the aromatic ring
(aromatic alcohols).
Table 2.9 Physical properties and the structure of the selected substances from PAHsa group
Aromatic Chemical Molecular Melting Boiling point Carcinogenicity
hydrocarbona Structural formula formula mass [g/mol] point [oC] [oC] Group (IARC)
Naphthalene C10H8 128.16 80.2 217.9 2B
Acenaphthene C12H10 154.21 93.4 279 3
Acenaphthylene C12H8 152.20 92.5 280

Fluorene C13H10 166.22 114.8 295 3
(continued)
37
38

Anthracene C14H10 178.22 215 339.9 3
Phenanthrene C14H10 178.24 99.2 340 3
Fluoranthene C16H10 202.26 107.8 384 3
Pyrene C16H10 202.26 151.0.2 404 3

Chrysene C18H12 228.28 258.2 448 2B
Benzo(a)anthracene C18H12 228.29 84 437.6 2B
Benzo(a)pyrene C20H12 252.32 176.5 495 1

Benzo(b) C20H12 252.32 168 357 2B

fluoranthene
(continued)
39
40

Benzo(e)pyrene C20H12 252.32 177.5 492 3
Benzo(k) C20H12 252,0.32 217 480 2B

fluoranthene
Benzo(j) C20H12 252.32 166 490 2B

fluoranthene
Dibenzo(a, h) C22H14 278.35 269.5 524 2A
anthracene
Benzo(g, h, i) C22H12 276.34 278 >500 3

perylene
Indeno(1,2,3-cd) C22H12 276.34 163.6 536 2B

pyrene
a
PAH identified as probable human carcinogens by the EPA [29]
41
Phenols are compounds in which hydroxyl –OH group is connected directly to

carbon from the aromatic ring. This structural difference is the reason of different
chemical properties of alcohols and phenols:
R OH
R′ C HO
phenol
R″
alcohols
where R′; R″ – alkyl groups.

Aliphatic Alcohols
Alcohols are classified as primary, secondary, or tertiary in dependence on the num-
ber of organic groups connected to the carbon atom with OH group:
Alcohols can be considered the derivatives of alkanes, in which the hydrogen

atom was substituted by –OH group, or the derivatives of water formed as the result
of exchanging the hydrogen atom with alkyl residue:
Names of alcohols (alcanols), according to the IUPAC, are formed by adding the
ending -ol to the name of the parent hydrocarbon, which is considered hydrocarbon
of the longest normal carbon chain, containing also the carbon atom connected
with –OH group. The numeration is selected in such way as to have the carbon atom
connected with –OH group of the smallest possible number.
Thus:
• In the group of monohydric alcohols:
2.4 Hydrocarbons with Functional Groups 43
• In the group of polyhydric alcohols:
Aromatic Alcohols
By the substitution of the hydrogen atom of the alkyl radical of any aliphatic alcohol
by the aryl radical, the aromatic alcohol is obtained:
CH3
CH2 OH CH OH CH2 CH2 OH
benzyl alcohol -phenylethyl alcohol -phenylethyl alcohol
Alcohols: α-phenylethyl alcohol and β-phenylethyl alcohol are isomers.

Phenols
Phenols are hydroxylic derivatives of benzene. Names of phenols according to the
IUPAC system are formed of the prefix “hydroxy-” and the hydrocarbon name.
Positions of substituents are marked by proper numbers:
OH OH OH OH
CH3
CH3
CH3
Phenol 2-methylphenol 3-methylphenol 4-methylphenol
o-cresol m-cresol p-cresol
Alcohols and phenols have significantly higher boiling points as compared with
other substances of similar molecular masses. This is due to hydrogen bonds form-
ing in a liquid state [10, 11]. The positively charged hydrogen atom from -OH group
of one particle is attracted by the negatively charged oxygen atom of another parti-
cle. This weak attraction between particles keeps them together, and in result the
aggregates of R–O–H particles are formed. These intermolecular influences must be
overcome by a particle freeing itself from the liquid state and entering into the vapor
state. Therefore the boiling point increases. The same effect occurs in the case
of water.
The solubility of alcohols and phenols in water is decided by the solvent interac-
tion with the polar hydrophilic –OH group and with nonpolar, hydrophobic hydro-
carbon fragment of a particle. In the case of short carbon chains (to C4), the
hydrophilic character prevails, and monohydric alcohols are mixed with water in
every ratio. Along with the chain length increase (above C4), water solubility of
alcohols decreases. Simultaneously, the particle polar character gives alcohols prop-
erties of good solvents of organic and inorganic substances.
Alcohols and phenols have acidic properties; however they are not acids, because
their water solutions are not acidic. Acidic properties of these substances are seen,
among others, in their reactions with metals (Eq. 2.30):
2 R − O − H + 2 Me → 2 R − O − Me + H 2
alcohol metal alcoholate or (2.30)

or phenol ( e.g.,Li,Na,Mg,Al ) metal phenolate
Alcoholates belong to strong bases (stronger than hydroxides of alkali metals).
Phenols indicate higher acidity than alcohols and are stronger acids than water, but
weaker than carboxylic acids. Different acidity of alcohols and phenols is related to
a different stability of substrates and dissociation products of these substances
(Eq. 2.31):
(2.31)

Basic properties of alcohols and phenols are revealed in esterification reactions,
in which these substances react with acids or their derivatives (in the case of phe-
nols). That time the hydrogen atom from –OH group is changed by the group of
atoms originated from an acid.
Alcohols are susceptible to oxidation. As a result of the primary alcohols, oxida-
tion aldehydes (or carboxylic acids) are obtained (Eq. 2.32), while oxidation of
secondary alcohols leads to the formation of ketones (Eq. 2.33):

[O] O [O] O
R CH2 OH R C R C
[H] [H]
H OH
(2.32)
primary alcohol aldehyde carboxylic acid
R [O] R
CH OH C O
R R + H 2O
(2.33)
secondary alcohol ketone
2.4.2 Ethers
Ethers can be considered to be water derivatives as well as alcohol derivatives. Two

hydrogen atoms in water are substituted by an alkyl or aryl group, while in alcohols
one hydrogen atom in -OH group is substituted by a radical, which means that two
organic groups are connected with the same oxygen atom: R–O–R. The bond sys-
tem C–O–C occurs in ethers, but not all substances containing this structural ele-
ment are counted to ethers.
When both substituents connected with oxygen – in ethers – are the same
(R = R′), ethers are called symmetric ethers, and when they are different (R ≠ R′),
ethers are called mixed ethers. In dependence on the character of substituents, there
are chain ethers, cyclic ethers, aliphatic saturated and non-saturated ethers, and aro-
matic and aliphatic–aromatic ethers. Ethers belonging to individual groups are
shown in Table 2.10.
Due to the presence of O atom in their molecules, ethers can form hydrogen
bonds with substances containing H atoms, e.g., with water. Ethers, due to their
polarity and ability to form hydrogen bonds, are good solvents of several organic
substances. Ethers are well soluble in strong mineral acids, forming unstable oxo-
nium salts. The common feature of all ethers is their alkalinity, being the result of
the free electron pair presence at the oxygen atom. Ethers are chemically passive
compounds, and they do not react with a majority of chemical reagents.
Table 2.10 Examples of aliphatic and aromatic ethers

CH3 − O − CH3 C2H5 − O − C2H5 CH3CH2 − O − CH = CH2
dimethyl ether diethyl ether ethyl vinyl ether
O - CH3 O CH3
CH3 C O
H
phenyl methyl phenyl ether phenyl isopropyl ether
ether
When working with ether, a special caution should be exercised since ether forms
explosive mixture with the air.
2.4.3 Aldehydes and Ketones
Aldehydes – organic substances having carbonyl group connected with at least one
hydrogen atom. Such group is also called the aldehyde group.
Carbonyl group – functional group occurring in several types of organic sub-
stances, consisting of a carbon atom connected by double bond with an oxygen atom.
carbonyl group C O
(Ar)R
aldehyde group C O where: R - hydrogen atom or alkyl group (R)
or aromatic group (Ar)
H
O O O CH3
O
H C CH3C CH3(CH2)2C
H CH3CHC
H H H
methanal ethanal butanal 2-methylpropanal
(formaldehyde)
O H O
CH
benzaldehyde 2- naphthalenecarboaldehyde
Ketones – substances containing carbonyl group connected with two car-

bon atoms.
(Ar) R1
general formula
C O where: R1, R2 - alkyl group
for ketone:
(Ar) R2 Ar - aromatic group
Names of ketones end by ending with -ne.
O CH3 C CH2 CH3 O
C
C O
H3C CH3 butanone benzophenone
propanone
Properties of the carbonyl group, which is highly reactive, decide on chemical

reactions of aldehydes and ketones. Aldehydes and ketones (up to four carbon
atoms) are fully or partially dissolved in water. They dissolve in a majority of
organic solvents. Aldehydes and ketones are very weak bases.
Oxidation of Aldehydes and Ketones
Aldehydes are easily oxidized to carboxyl acids, according to the formula (Eq. 2.34):
O O
[O]
CH3 C CH3 C2H5 C OH
(2.34)
propanone propanoic acid
Oxidation occurs easily under an influence of such substances as Na2Cr2O7,

KMnO4, and HNO3. Aldehydes undergo slow oxidation also under an influence of
atmospheric oxygen.
Ketones do not subject to influences of a majority of oxidizers but undergo fis-
sion reactions under an influence of hot alkaline solution of KMnO4. C–C bond, at
the carbonyl group, undergoes tearing, and carboxylic acids of shortened carbon
chains are formed (Eq. 2.35):
CH3 C CH3 K2Cr2O2 4H2SO4

propanone
O O
CH3 C H C K2SO4 Cr2(SO4)3 4H2O
H OH (2.35)
acetic acid formic acid
Hydrogenation of Aldehydes and Ketones

Aldehydes and ketones are hydrogenated (reduction of carbonyl group) in the pres-
ence of catalysts such as palladium, activated platinum, and nickel. Hydrogenation
of aldehydes leads to the formation of primary alcohols, while hydrogenation of
ketones leads to secondary alcohols.
As an example (Eq. 2.36a, 2.36b):
(2.36a)

(2.36b)

Lower aldehydes, especially formaldehyde and acetaldehyde, are characterized
by a significant inclination to polymerization, in which particles of the backbone –
built of alternately repeating carbon and oxygen atoms – are formed. In dependence
on conditions, formaldehyde is polymerizing to linear products of various molecu-
lar masses or forming ring-trimmer called trioxane (Eq. 2.37).
O
(CH2O)3 H2C CH2
O O
CH2
(2.37)
formaldehyde 1,3,5, - trioxane
2.4.4 Carboxylic Acids
Connection of carbonyl group with hydroxyl one forms the carboxylic group char-
acteristic for carboxylic acids:
O
C
OH
carboxylic group
A mutual influence of carbonyl and hydroxyl group, situated at one carbon atom,
is the reason that properties of carboxylic acids are neither the sum of ketone and
alcohol properties nor the sum of aldehyde and ketone properties (Table 2.11).
Carboxylic acids have boiling points much higher than other compounds of simi-
lar molecular masses. This temperature increase is the result of the fact that in the
liquid state, particles of carboxylic acids are strongly associated due to intermolecu-
lar hydrogen bonds. These bonds are much stronger in acids than in alcohols.
Aliphatic acids, to C4 (e.g., formic, acetic) are well water soluble. As far as the
hydrophobic acid radical increases, the water solubility decreases.
Chemical Properties of Carboxylic Acids
Carboxylic acids in water solutions are dissociating, according to the formula
(Eq. 2.38):
O O
R C H2O R C H3O+ (2.38)
OH O-
Carboxylic acids influence metals causing their oxidation and the evolution of
free hydrogen (Eq. 2.39):
2CH 3 COOH + Zn → ( CH 3 COO )2 Zn + H 2 (2.39)

They are reacting with hydroxides, oxides, and metal carbonates (Eq. 2.40a,
2.40b, 2.40c):
CH 3 COOH + NaOH → CH 3 COONa + H 2 O (2.40a)
2CH 3 COOH + HgO → ( CH 3 COO )2 Hg + H 2 O (2.40b)

2CH 3 COOH + CaCO3 → ( CH 3 COO )2 Ca + H 2 O + CO2 (2.40c)

Carboxylic acids are weaker acids than mineral ones, however stronger than car-
bonic acid.
Carboxylic acids, apart from a few exceptions, are resistant to oxidizers. Heating
of some carboxylic acids causes their decomposition and evolution of carbon diox-
ide (decarboxylation reaction) (Eq. 2.41a, 2.41b):
Table 2.11 Examples of carboxylic acids (monocarboxylic acids)
50
O O O
C C CH3 C
H OH CH3 OH CH2 OH
formic acid acetic acid propionic acid

O OH O O
C OH
OH
N
H
benzoic acid nicotinic acid cyclopentanecarboxylic acid
COOH COOH
OH
hydroxybenzoic acid naphthoic acid

Dicarboxylic acids
(CH2)2(COOH)2 (CH2)3(COOH)2 (CH2)4(COOH)2

succinic acid glutaric acid adipic acid
O OH
HO O
C6H4(COOH)2 C6H4(COOH)2 (COOH)2
phthalic acid terephthalic acid oxalic acid
51
(2.41a)

O
C
OH ΔT
CO2
C CH3 C CH3
O O (2.41b)
3-phenyl-3-oxopropanoic 1-phenyl-ethanone
When −OH group in carboxylic acid is substituted by other group, the following
can be obtained: acid chlorine (−Cl), acid anhydride (−OCOR), amide (−NH2), or
ester (−OR) (Fig. 2.4).
2.4.5 Esters of Carboxylic Acids
Esters constitute the group of substances, derivatives of carboxylic acids in which

hydrogen atom is substituted by the ester group.
O
C
R OH
carboxylic
acid O
O
C
C R NH2
R Cl amide
acid chloride O O O
C C C
R O R R OR
anhydride cster
Fig. 2.4 Derivatives of carboxylic acid

O
C
O
Ester group
Ester is formed in the reaction of carboxylic acid with alcohol. This is a revers-
ible reaction, which – after a longer time – achieves the state of equilibrium
(Eq. 2.42):
O O
H
R C R1 OH R C H2O
OH OR1 (2.42)
acid alcohol ester water
This reaction is catalyzed by strong mineral acid (e.g., sulfuric), which simulta-
neously binds water formed in this reaction.
A majority of aliphatic and aromatic carboxylic acids undergo esterification
(Eq. 2.43):

O O
CH2 CH2 H+ CH2 CH2 +

C + C H2O
CH2 CH3 CH2 CH3
CH3 OH OH CH3 O
acetic acid + butyl alcohol = ester: butyl acetate

O OH O
OH
O
+ =
(2.43)
benzoic acid + phenol = phenyl benzoate
The hydrolysis reaction belongs to the most important transformations of esters.
It can occur as:
• Reversible acidic hydrolysis (Eq. 2.44):
(2.44)

• Irreversible basic hydrolysis (saponification) where carboxylic acid salt and
alcohol are products (Eq. 2.45):
O O
R C + NaOH R C + R1OH (2.45)

OR1 ONa

When alcohol and inorganic acid take part in the reaction, inorganic ester is
formed (Eq. 2.46):
CH2 HNO3 CH2 N

CH3 OH CH3 O O
(2.46)
Esters of dicarboxylic acids
CH₃-OOC-(CH₂)₃-COO-CH₃ C2H5- OOC-(CH₂)2- COO-C₂H₅.
dimethyl ester of glutaric acid dimethyl ester of succinic acid
CH₃-OOC-(CH₂)4-COO-CH₃
dimethyl ester of adipic acid
Esters are very weak bases, only slightly stronger than aldehydes and ketones.
They also have a weak acidic character.
Ester in reaction with ammonia is turning into amide and alcohol (Eq. 2.47):
R − COO − R ′ + NH 3 → R − CO − NH 2 + R ′ − OH
(2.47)
ester ammonia amide alcohol
Fats – are esters of higher aliphatic carboxylic acids and trihydroxide alcohol
(glycerin). The general formula is as follows (acid radicals R1 ≠ R2 ≠ R3) (Eq. 2.48):
(2.48)

Examples of higher fatty acids:
Saturated: Unsaturated:
Palmitic acid CH3(CH2)14COOH Oleic acid CH3(CH2)7CH = CH(CH2)7COOH
Stearic acid CH3(CH2)16COOH Linoleic acid
Arachic acid CH3(CH2)18COOH CH3(CH2)4CH = CHCH2CH=CH(CH2)7COOH
An example of obtaining solid fat is given below:
CH2 OCOC15H31
CH2 OH
H
CH OH 3C15 H31COOH CH OCOC15H31 3H2O
CH2 OH CH2 OCOC15H31
glycerol palmitic acid glycerol tripalmitate (solid fat)
Waxes – are esters of saturated fatty acids (often containing more than 20 carbon
atoms) and alcohols of not branched long chains (up to more than 30 carbon atoms).
The general formula of waxes:
2.4.6 Nitrogen Organic Compounds
Amines
Amines can be considered derivatives of ammonia, in which one or a few hydrogen
atoms are substituted by alkyl (R) or aryl (Ar) radicals. Amines are classified on the
bases of the number of substituents connected with nitrogen atom.
Orders of amines:
H R1 R1 R4
R1
H N H N H N N
R3 N
R1
H H R2 R2 R2 R3
ammonia primary secondary tertiary quaternary
amine amine amine amine
Aliphatic Amines
H3C–NH2 Methylamine (a primary amine)

CH3–CH2–NH2 Ethylamine (a primary amine)
H3C–NH–CH3 Dimethylamine (a secondary amine)
CH3–CH2–NH–CH3 Ethylmethylamine (a secondary amine)
Trimethylamine (a tertiary amine)
Aliphatic amines form salts with organic and inorganic acids (Eq. 2.49):
RNH 2 + H + = RNH 3 + ( alkyl ammonium cation ) (2.49)

They undergo electrolytic dissociation in water (Eq. 2.50):
RNH 2 + H 2 O = RNH 3 + + OH − (2.50)

Primary and secondary amines undergo alkylation and secondary and tertiary
amines are formed (Eq. 2.51):

RNH 2 + R – X = R 2 NH 2 X ( ammonium salt ) (2.51)
X – halogen or acid radical of sulfuric or sulfonic acid.

Primary and secondary amines are sensitive to the influence of various oxidative
substances.
Amines have relatively low boiling points. Aliphatic amines are better water
soluble than alcohols. Amines of low molecular masses have characteristic smells,
similar to the fish smell. Amines are widely present in nature. Trimethylamine
occurs in animal tissues. Nicotine is a known substance contained in tobacco.
Cocaine is a well-known stimulant.
Aromatic Amines
aminobenzene dimethylaniline naphthylamine.

Amines have basic properties, in a similar fashion as ammonia, in addition to
which aliphatic amines indicate higher basic properties than ammonia while aro-
matic amines weaker basic properties than ammonia.
Acid Amides
Acid amides are derivatives of carboxylic acids, in which –OH group from the car-
boxyl group is substituted by –NH2 group:
O O
R C R C
O H N H
H
carboxylic acid amide of carboxylic acid
Acid amides are divided into I, II, and III order (R1 and R2 – alkyl and aryl
substitute):
O O O
R1 C R1 C R1 C
N H N H N R3
H R2 R2
Primary amide secondary amide tertiary amide
Examples of acid amides:
O O O
O CH3 C
N H C C
C NH2 NH2
H NH2 H OH
amide of formic acid amide of acetic acid amide of benzoic acid amide of salicylic acid
Amides undergo hydrolysis, both acidic and basic.

Hydrolysis in the acidic environment under an influence of strong inorganic
acids (Eq. 2.52):

O O
CH3 C H2SO4 H2O CH3 C NH4HSO4
NH2 O
amide of acetic acid sulfuric acid (VI) acetic acid acidic ammonium (2.52)
sulfate (VI)
Hydrolysis in the basic environment under an influence of alkali metals
(Eq. 2.53):

O O
CH3 C NaOH CH3 C NH3
NH2 ONa
(2.53)
amide of acetic acid sodium hydroxide sodium acetate ammonia
Urea
Amide derivatives of carbonic acid constitute the separate group. Carbonic acid, due
to the presence of two carboxyl groups in its particle, can form organic derivatives,
e.g., urea (diamide of carbonic acid):
O O
C C
HO OH H2N NH2
carbonic acid urea (carbamide)
Urea is a colorless crystalline substance and well water soluble giving solution
of neutral pH. It undergoes hydrolysis:
• In an acidic environment under an influence of strong inorganic acids (Eq. 2.54):
(2.54)

• In the basic environment under an influence of alkali metals (Eq. 2.55):
(2.55)

As the result of the condensation of two urea particles, the diurea particle called
biuret, which contains peptide bond, is formed (Eq. 2.56):
(2.56)

Nitro Compounds
Nitro compounds are organic compounds containing nitro group −NO2, in which
the nitrogen atom is directly connected with the carbon atom. Aliphatic nitro com-
pounds are divided into primary, secondary, and tertiary compounds in dependence
of the order of carbon with which NO2 group is connected.
General formulas of aliphatic nitro compounds of I, II, and III order:
Examples of nitro compounds:
Nitro compounds are usually difficult to dissolve in water. Their solubility

decreases when molecular mass increases. Aromatic nitro compounds are high-
boiling liquids or solids insoluble in water. Nitro compounds are reduced to primary
amines [4, 9]. The most important representative of nitro compounds is 2,4,6-trini-
trotoluene, i.e., C6H2(NO2)3CH3. It is obtained by two-stage nitration of toluene by
a mixture of sulfuric and nitric acids.
Nitriles
Nitriles are organic substance derivatives of hydrogen cyanide, containing nitrile
group –C ≡ N . Their general formula is R –C ≡ N, where R means either alkyl
or aryl.
Lower nitriles are quite well water soluble:
In acidic or basic environments, nitriles hydrolyze into carboxylic acids

(Eq. 2.57):
R − CN + 2H 2 O → RCOONH 4

RCOONH 4 + HCl → RCOOH + NH 4 Cl (2.57)

Nitriles subjected to reduction form primary amines:
R − CN + 2H 2 → R − CH 2 − NH 2

2.4.7 Sulfuric Organic Compounds
Sulfuric acids are substances containing sulfo group SO2OH. This group has a
highly acidic character, of a power comparable with a power of inorganic acids. One
compound can contain a few sulfo groups forming polysulfuric acid.
SO3H SO3H SO3H

SO3H
H3C CH3
CH3
benzenesulfonic p-toluenesulfonic m-toluenesulfonic o-toluenesulfonic

acid acid acid acid
Aliphatic sulfonic acids are obtained, among others, in reaction of sodium sulfite
with alkali chlorides (Eq. 2.58):
R − Cl + Na 2 SO3 → R − SO2 OH (2.58)

Aromatic sulfonic acids are obtained by direct sulfonation by concentrated sul-
furic acid or oleum. Sulfonation reaction of toluene by sulfuric acid (Eq. 2.59):
CH3 CH3
H2SO4
H2O
SO3H
toluene p-toluenosulfonic (2.59)
acid
Evolved water dilutes sulfuric acid and thereby influences the reaction inhibi-
tion. Therefore this reaction is often performed at temperatures above 100 °C.
A specific meaning of sulfonic acids is based on the fact that sulfonic group can
be easily substituted by other functional groups.
At melting sodium or potassium salts of aromatic acids with strong hydroxide
(NaOH), the exchange of the sulfonic group into hydroxyl one occurs. In result
phenol and sodium sulfate are formed (Eq. 2.60):
C6 H 5 – SO3 Na + NaOH → C6 H 5 OH + Na 2 SO3 (2.60)

2.5 Polymers and Polymerization
2.5.1 Polymers and their Properties
Polymer is a high-molecular substance, built of organic or inorganic macromole-

cules. It consists of a large number of joined together basic structural units – mono-
mers. The number of monomers can be from 10,000 to 1,000,000. In general, the
polymerization reaction can be written as:
nA + nB → A·B·A·B·A·B·A → [ A B ] p
monomer monomer polymer mer
where p – polymerization degree.

Macromolecules can be joined together by means of covalent, hydrogen, ionic,
or coordinate bonds. The kind of bonds connecting macromolecules decides on
physical–chemical, mechanical, processing, and functional properties of poly-
mers [12].
Polymerization degree – number of monomers (including also the chain begin-
ning and end) contained in one macromolecule.
On account of their origin, polymers are divided into [13, 14] (Fig. 2.5):
• Natural polymers (biopolymers) are high-molecular substances produced by
organisms: proteins (keratin, collagen, natural silk, casein), nucleic acids (DNA,
deoxyribonucleic acid, and RNA, ribonucleic acid), natural rubbers (polyiso-
prene, natural rubbers of vegetative origin), and polysaccharides (e.g., cellulose,
starch, glycogen, chitin, chitosan, pectin).
• Synthetic polymers are polymers chemically produced of monomers.
• Modified polymers are natural or synthetic polymers, which surface structure or
the whole mass was changed by means of chemical or physical way.
The term plastics determines material, in which, apart from the basic component,
polymer, additional components (fillers, plastifiers, stabilizers, dyes, and others) are
scattered.
2.5 Polymers and Polymerization 63
Fig. 2.5 Basic division of polymers, adapted from [15]
In respect of their physical structure, polymers can be divided into:

• Thermoplastic polymers: of a linear or branched structure (crystalline or amor-
phous), usually soluble in organic solvents, are melting and flowing, and can be
heated (below the degradation temperature) and cooled several times. A majority
of polymerizing materials belong to thermoplasts and – in addition – polyam-
ides, polycarbonates, polysulfones, thermoplastic derivatives of cellulose, and
polyesters.
• Thermosetting polymers and chemically cured polymers (duroplasts): occur only
in the glass state, have a high cross-linking degree, and are insoluble in organic
solvents. They do not melt and flow and, when heated above a thermosetting
temperature, undergo usually a thermal degradation. The most important repre-
sentatives of this group of materials are phenol–formaldehyde resins and amino
plastics.
Phase transformations of polymers, the so-called secondary transformations:
occur at the determined temperature, characteristic for the given polymer. Thus,
there is:
• Brittle temperature Tb – temperature of transition from the brittle glass state into
glass state with forced elasticity.
• Flow temperature Tf – temperature of transition from the elastic state into plastic
state (and vice versa).
• Glass temperature Tg – temperature of transition from the glass state into elastic
(and vice versa).
• Melting temperature Tm (melting is the phase transformation of the first kind) –
temperature of transition from the crystalline state into liquid state.
Polymers are produced by:
• Chain polymerization (previous name: polyaddition) – it means joining of sev-
eral monomer particles into one macromolecule, without emitting side products.
• Gradual polymerization (previous name: polycondensation) – it means joining of
several particles containing reactive groups into one macromolecule with emit-
ting low-molecular side products (e.g., HCl, H2O, etc.).
• Synthesis of macromolecules by living organisms – gradual polymerization
which is much slower than the chain polymerization.
• Chemical modification of natural or synthetic polymers.
The kind and properties of the formed polymer depend mainly on the applied
monomer. As the result of the polymerization of two functional monomers, contain-
ing in their particles either one double bond or two reactive groups, the linear poly-
mers, which can melt and dissolve in solvents of a similar polarity, are formed
(Fig. 2.6).
Fig. 2.6 Dependence of the polymerization degree on the conversion degree of the chain polym-
erization (curve 1) and gradual polymerization (curve 2). (Adapted from Ref. [16])
2.5.2 Polymerization: Kinds and Mechanisms
Polymerization is the chemical process in the result of which the polymer is obtained
from monomers. This process occurs by multiple repetitions of a simple chemical
reaction, which constitute the so-called polyreaction.
Synthetic polymers are divided, in dependence on their synthesis process, into
polymers formed according to the mechanism [5, 15] of:
• Chain polymerization (chain or additive polymers):
Each reaction of chain elongation in the chain polymerization is related to join-
ing only one monomer particle. Its main property is the occurrence of the reactive
place (called the active center) in a particle – able to join the substrate – generally at
the chain end [17]:
−M ∗ + M → −M − M ∗
The created, reactive intermediate product attacks the next particle with C=C
bond, and the new reactive product is formed, which attacks the next monomer
particle, etc. The active center constitutes the most often radical, cation, anion, or a
strongly polarized covalent bond.
On the industrial scale, by means of the chain polymerization can be obtained,
among others, polystyrene, polyethylene, and polyvinylchloride.
Generally, monomers with multiple bonds (double, triple) or reacting with the
ring opening undergo the chain polymerization.
The chain polymerization is characterized by a lack of a direct dependence
between the polymerization degree and the conversion degree of the monomer func-
tional groups.
The following stages can be singled out in the chain polymerization process [18]:
• Initiation of the polymerization.
• Increase of the polymer chain (propagation).
• Chain ending (termination).
Initiation reaction (formation of active centers) – the monomer particle is sup-
plied with energy (e.g., by heating or lightening) necessary for its activation (e.g.,
for a double bond breaking). Sometimes a special chemical substance, the so-called
initiator which undergoes disintegration, is added to the system. As the result, an
unstable intermediate product is formed (radical or ion). It connects itself with the
monomer particle and starts the chain increasing period leading to macromolecule
formations. The polymer chain increase can be stopped either by destruction of
active centers or by transferring the activity from the macromolecule being formed
into the monomer or solvent particle (the so-called chain transfer). Such chain trans-
fer causes an increase of the next macro-radical, while the polymerization rate is not
changed. Usually reactions of the chain ending or chain transfer occur spontane-
ously, due to various chemical reactions with solvent, random contaminations,
oxygen, or growth controllers introduced on purpose. The chain process is finally

ended in the reaction absorbing a radical, e.g., the recombination reaction.
In dependence on the element initiating the chain polymerization process, the
following chain polymerizations are singled out:
• Free radical polymerization.
• Cationic polymerization.
• Anionic polymerization.
• Coordination polymerization.
• Polymerization with a ring opening.
Radical Polymerization
Radical polymerization is the most useful industrial method of obtaining – on a
large scale – different kinds of polymers. More than 50% of all plastics are pro-
duced by this method.
The radical polymerization mechanism contains several elementary processes,
as the result of which a polymer is obtained from a monomer [15].
Initiation of Polymerization
Initiation of the radical polymerization reaction occurs by means of free radicals
(R•), which after joining with a monomer particle (M) form initiation radicals (RM•):
R • + M = RM•
These radicals react with successive monomer particles causing a fast growth of
polymer macro-radicals (RMn + 1)
RM• + nM = RM n +1

Radicals are electrically neutral fragments of particles with an individual
unpaired electron. They are usually unstable, but are characterized by a high chemi-
cal activity. Reactions with a participation of radicals can lead either to forming of
other radicals, i.e., new particles with an unpaired electron, or to a decay of the radi-
cal active center. The radical sources constitute mainly initiator particles, which
undergo thermal or photolytic dissociation. Free radicals are also formed in redox
reactions.
The radical polymerization of styrene consists of the following stages:
(a) Radical formation of dibenzoyl peroxide, which at temperatures 40–90 °C
undergoes thermolysis to benzoyl radical and then to phenyl radical [10, 15, 18,
19]. Both radicals are taking part in the polymerization (Fig. 2.7).
(b) Beginning of the chain formation: benzoyl and phenyl radicals formed in the
decomposition of the initiator are joining the monomer particle in the double
bond place, forming a new radical. New radicals initiate the chain growth reac-
tion, with various rates depending on their activity (Eq. 2.61).
.
C O O C 2 C O. 2 + 2 CO2
O O O
dibenzoyl peroxide benzoyl radical phenyl radical
Fig. 2.7 Thermal decomposition of dibenzoyl peroxide
(c)
R CH2 CH R CH2 CH
(2.61)
Radical Styrene
where R·– initiator radical.
Free radicals, being initiators, can be also created in a photochemical process.
This process is based on absorption of the light energy quant by a monomer particle
and its transition into the excited state. A main advantage of photochemical reac-
tions is their total independence from a temperature.
Sometimes the free radical polymerization can be thermally initiated without
using initiators.
(d) Chain growth, i.e., a propagation, is based on successive joining monomer par-
ticles with the growing macro-radical. The chain growth rate depends on mono-
mer reactivity, radical reactivity, as well as viscosity of polymerizing mixture.
The chain growth rate is very high (polymer particle of 10,000 monomer parti-
cles is formed in 1 s) (Eq. 2.62):
R CH2 CH CH2 CH R CH2 CH CH2 CH
(2.62)

(e) The chain growth end in the radical polymerization process can occur due to:
• Recombination of radicals – the chain growth is stopped by a mutual
recombination reaction of two growing chains, whereas the formed macro-
molecule has its molecular mass equal to the sum of molecular masses of
both radicals (Eq. 2.62):
•
2R CH2 CH R CH2 CH CH CH2 R
• •
R CH2 CH CH2 CH + R R CH2 CH CH2 CH R
• Disproportioning reaction of macro-radical causing the hydrogen atom transfer

from one macro-radical to the other:

• • •
R CH2 CH CH2 CH + R CH2 CH CH2 CH
R CH2 CH CH CH + R CH2 CH CH2 CH2
(2.63)

• The chain activity transfer caused by the collision with no active particle being
in the environment of the reaction (Fig. 2.8).
Ionic Polymerization
Catalysts of the ionic polymerization constitute appropriate anions or cations. Their
catalytic activity is the acceleration of reactions. They are temporally joining with
the reagents but do not enter into the final product.
Fig. 2.8 Formation of

polystyrene H H
CH CH2 H C
C H
cat.
H
n
styrene polystyrene
Anionic Polymerization
Initiators of the anionic polymerization are alkali metals (Li, Na, K), hydrides of
alkali metals, and ions of alkali metals with aromatic organic compounds (e.g.,
sodium naphthalene, sodium benzene) [13, 15].
The anionic polymerization course is shown in Fig. 2.9, the example of styrene,
where sodium amide NaNH2 is its initiator (reaction proceeds in liquid ammo-
nia) [18].
Sodium amide dissociates, according to a reactions (Fig. 2.9):
Stage III – the growth end – negative macroion is neutralized by proton or the
charge is transferred on a monomer or solvent:
Cationic Polymerization
The cationic polymerization constitutes the process of a monomer or a mixture of
monomers transferring into a polymer, according to the cationic mechanism, in the
presence of catalysts.
-
O O
H2N CH2 CH CH2 CH . Na H
C6H5 m C6H5
H2 N CH2 CH
CH2 CH2 NaNH2
C6H5
m C6 H5
Fig. 2.9 The anionic polymerization course at the example of styrene

Catalysts of this reaction are sulfuric acid, perchloric acid, Lewis acids, or
Friedel–Crafts catalysts such as AlCl3, BF3, and TiCl4. The activity of these last
catalysts increases in the presence of coinitiators (co-catalysts), i.e., substances
being the source of protons (H+ ions). As co-catalysts can be applied: water, hydro-
chloric acids (e.g., HClO4). An excess of a coinitiator leads to a premature chain end.
The cationic polymerization process of isobutylene with BF3 as a catalyst and
water as the initiator is shown below [15].
During the first stage, the substance which dissociates into ions is formed
(Eq. 2.64):
BF3 + H 2 O → [ BF3 • H 2 O ] ↔ H + + [ BF3 OH ]

−
(2.64)

The formed H+ proton is joining the monomer and initiates the reaction:
CH3 CH3
H H2C = C C O
CH3 CH3
During the chain increase, the positive macroion is created (Eq. 2.65):

CH3 CH3 CH3 CH3 CH3
O
H3 C C O CH2 C CH3 C CH2 C O n CH2 C
CH3 CH3 CH3 CH3 CH3
CH3 CH3 CH3
CH3 C CH2 C CH2 C O
(2.65)
CH3 CH3 CH3

The reaction end occurs because the proton splits, due to a decreasing activity of
large ions. This causes the positive ion regeneration and ending of the polymeriza-
tion process.
Monomers polymerizing according to the cationic mechanism are, among oth-
ers, isobutylene, styrene, and vinyl ethers.
Gradual Polymerization (Condensation Polymers)
The gradual polymerization (previous names: polycondensation or polycondensa-
tion polymerization) is the synthesis method, alternative in relation to the chain
polymerization. There are two basic kinds of gradual polymerization: polyconden-
sation and polyaddition. The characteristic feature of polycondensation is
obtaining, apart from polymers, low-molecular products such as H2O and HCl. Such
effect does not occur in the polyaddition reaction.
In macromolecules of the created product, the main chain contains, apart from
carbon, atoms of other elements such as oxygen, nitrogen, phosphor, boron, or silica
[19]. In contrast to the chain polymerization, the gradual polymerization occurs – as
the name implies – gradually. Temporary, stable products able to be separated are
formed in each stage of this process. The gradual polymerization is characterized by
the lack of the chain ending reaction.
The macromolecule chain is growing slowly. Its kinetics depends on tempera-
ture, removal rate of low-molecular side products, as well as the amount and char-
acter of the catalyst (usually on the hydrogen ion concentration).
In the gradual polymerization, a macromolecule increases gradually due to direct
reactions of functional groups occurring in substrates and later at the end of a grow-
ing chain. Larger and larger particles, formed successively from substrates, can join
with each other and with substrates:
n A R A + n B R B → A R n B + n AB

where: AB = H2O, HCl.
By the gradual polymerization method, the following polymers are produced, on
the industrial scale, polypropylene, polyethylene, polystyrene, and vinyl
polychlorinated.
Monomers (substrates) in the polymerization process constitute the most often
substances containing unsaturated bonds (mainly C=C).
Comparison of the gradual and chain polymerization is presented in Table 2.12.
The gradual polymerization is a very important technological process of obtain-
ing several, widely applied, polymers, e.g., polyesters, polyamides, phenolic and
urea resins, or silicones (Table 2.3). Some of them found the application in the
foundry industry as synthetic resin binders. To this group belong phenol–formalde-
hyde, urea–formaldehyde, and furan resins. Also biopolymers, such as nucleic acids
and proteins, are produced by living organisms in the gradual polymerization.
Nearly all polymers which are obtained in the chain polymerization can be also
obtained by means of the gradual polymerization.
The gradual polymerization is a multiple condensation reaction of functional
groups, which – at the process initiation moment – are present in a monomer and
then at the ends of growing chains: for example polyester is formed as a result of a
condensation reaction with a participation of carboxylic and hydroxyl functional
groups (polyesterification). The necessary condition of the polymer formation is the
presence of at least two functional groups in each particle.
Coordination Polymerization
The coordination polymerization is a new type of synthesis of macromolecular sub-
stances leading to achieving polymers of regular spatial structures. This is a cata-
lytic process, based on the formation of coordination connections between a catalyst
Table 2.12 Comparison of the gradual and chain polymerization

Chain polymerization Gradual polymerization
Monomer contains functional groups (e.g., Monomer contains functional groups able to a
double bonds) requiring the activation direct reaction
Initiation of polymerization is necessary Initiation of polymerization is not necessary
Polymerization product of a large molecular Polymerization product of a large molecular mass
mass is obtained already during initial is obtained only at high conversion degrees
polymerization stages
There is a lack of side products Side products, e.g., water, occur
Chemical composition of a polymer and Chemical composition of a polymer and monomer
monomer is the same is different
Polymerization degree is equal to the Polymerization degree is characterized by the
quotient of molar masses of a polymer and polymer average molar mass
monomer
Polymerization process is usually Polymerization process is usually reversible
irreversible
High purity of a monomer is required Number of functional groups in a monomer is
important
Time of the polymerization reaction Time of the reaction is essential in obtaining
significantly influences its yield but only polymers of a high molar mass
slightly the molar mass
and monomer. Catalysts of the Ziegler–Natty type (TiCl4, TiBr4, VCl3, CoCl2) are
widely applied in the industry.
The coordination polymerization mechanism can differ, in dependence on the
applied coordination catalyst. When metal halide – in which metal is at a higher
oxidation degree – will be used in the catalytic complex synthesis, the coordination-
radical polymerization will occur. This polymerization is caused by the free radical
formation in the reduction reaction (Eq. 2.66) [15, 19]:
TiCl 4 + AlR 3 → RTiCl3 + AlR 2 Cl

RTiCl3 → R • + TiCl3 (2.66)
R • + nM → polymer

Free radicals “R•” initiate the polymerization process.
2.5.3 Inorganic Polymers
Inorganic polymers are as follows [15]:

• Hard materials (diamond, boron carbide B4C, silicon carbide SiC).
• Fibers (glass, asbestos).

• Structural materials (window glass, Portland cement, aluminum silicate).
• Mineral fillers (metal oxides, soot, graphite).
In the case of polymers built of silicon, phosphor, and boron, which constitute
the skeleton of the main chain, it can be assumed that these are inorganic–organic
polymers.
Silicon carbide ( (β-SiC carborundum) is a crystalline polymer completely inor-
ganic. It has a low density and is thermally stable up to 1600 °C. It is very hard and
highly mechanically resistant.
2.5.4 Inorganic–Organic and Organo-Metallic Polymers
Inorganic–organic and organo-metallic polymers have the following advantageous

properties:
• Density and stability similar to organic polymers.
• Strength and electricity conduction comparable to metals.
• Low density, high thermal resistance, as ceramics.
These polymers do not have disadvantages of:
• Organic polymers (low resistance to oxygen, organic solvent, high
temperature).
• Metals (high density, susceptibility to corrosion).
• Ceramics (brittleness, difficult processing).
Polysiloxanes (silicones) contain – in the main chain – siloxane (− Si - O – Si –)
group, in which silica atoms are joined by covalent bonds with oxygen atoms.
Hydrogen atoms or hydrocarbon molecules can be connected to silica atoms.
R
O
Si
siloxan structure, R – substitutes: − H; − CH3, − C2H5.

Polysilanes have silane (–Si – Si –) group in their main chain. Any substitutes
can be connected to silicon atoms.
H3C CH3
Si
H3C CH3
tetramethylsilane
The most important organo-metallic polymers are coordination polymers of fer-

rous, wolfram, chromium, molybdenum, zirconium, etc.
2.5.5 Degradable Polymers
A large production of plastics as well as impossibility of a total usage of their wastes

is the reason that their significant part is located on dumping grounds. In order to
limit the amount of stored wastes and to relieve the environment from excessive
amounts of wastes, studies on the development of such plastics which – after being
used – would undergo degradation during storage in the natural environment are
carried out.
Since the degradation of polymers can occur under an influence of radiation or
microorganisms or enzymes, the degradable polymers can be divided into [19]:
• Biodegradable polymers.
• Photodegradable polymers.
• Composites of biodegradable polymers.
Biodegradable polymers are natural polymers or polymers obtained by modifica-
tions of natural polymers as well as polymers produced by various methods of
chemical synthesis and in biotechnological processes. Biodegradable plastics are
manufactured either of renewable raw materials (poly(lactic acid) (LAc) – polylac-
tide (PLA), poly(glycolic acid) (PGA), modified starch) or of raw materials origi-
nated from the crude oil processing (polycaprolactone (PCL)). A significant
advantage of biodegradable polymers is a possibility of the utilization of spent prod-
ucts and other wastes by means of the composting method where they are subjected
to influences of various microorganisms. The polymer biodegradation process is a
very complex process and can occur in many ways. It can be assumed that the bio-
degradation process occurs in two stages [20].
• Stage 1. Depolymerization of macromolecules into shorter chains (material frag-
mentation and weakening of its cohesiveness), mainly as a result of mechanical
operations caused by microorganisms. This stage occurs usually out of organism
due to the polymer chain size and insolubility of several polymers.
• Stage 2. Represents the mineralization process, when sufficient amounts of small

oligomers are formed and transported to cells where they are subjected to bio-
assimilation by microorganisms, leading – in effect – to a partial
mineralization.
The biodegradation can occur according to two schemes, in dependence on the
oxygen presence:
• Aerobic biodegradation (in an oxygen presence).
• Anaerobic biodegradation (at a lack of oxygen).
The final product of the biodegradation process is the biomass (organic matter
mass) with emissions of water and gases, such as CO2, CH4, and NH3. The complete
biodegradation or mineralization occurs when there are no residues, i.e., when the
initial material is totally transformed into gases or salts. These changes cause wors-
ening of physical and mechanical properties.
A majority of synthetic polymers are not biodegradable. The following factors
decide the biodegradation course and rate: microorganism kind, material type, and
environmental conditions, which are the most important (temperature, pH, humid-
ity, oxygen, and light access) [14].
Poly(lactic acid) (PLA) is a completely biodegradable polymer. The initial sub-
strate for its synthesis is lactic acid (LAc), obtained in the fermentation process of
carbohydrates originated from potatoes, corn, and sugar beet.
Two methods of obtaining poly(lactic acid) are used:
• Polymerization with opening the cyclic ring of lactide (Fig. 2.10).
• Polycondensation of lactic acid (Fig. 2.11).
Fig. 2.10 Schematic presentation of the poly(lactic acid) formation by the polymerization method
with opening the lactide ring
HO O –H2O O CH3 O
HO O
H3C OH O OH
CH3 O nCH
3
lactic acid polylactic acid
Fig. 2.11 Schematic presentation of the poly(lactic acid) formation by the polycondensation of
lactic acid
Photodegradable Polymers
Polymers are aging with time, which is revealed by the degradation process consist-
ing of a molecular mass decrease, changes of the chemical structure, and in conse-
quence changes of physical–chemical properties. The factor causing these changes
is often UV radiation originated, e.g., from the sunlight. Under natural conditions,
different physical factors are important in the polymer photodegradation: sunlight,
temperature, humidity, and atmospheric components (contaminations). When the
air is present, secondary reactions occur with oxygen, and then the polymer photo-
oxidation occurs.
Photodegradable polymers, among which the most important are polyolefins, are
mainly applied in the production of packages.
Partially Biodegradable Materials
One of the ways of obtaining thermoplastic biodegradable materials is the physical
modification of polyolefins or other vinyl polymers by mixing them with natural
biodegradable polymers. These natural polymers applied for modifying synthetic
polymers are cellulose, lignin, starch, alginates, and chitin.
In the case of synthetic polymers, their degradation constitutes the process due to
which macromolecules are disintegrated into smaller fragments, which worsens
polymer properties. A special case of the polymer degradation is depolymerization
leading to the monomer formation. The degradation of polymers occurs under an
influence of physical, chemical, or biological factors.
Physical factors causing the degradation of polymers are increased temperature,
ionizing radiation (X-ray radiation), sunlight, ultrasounds, and mechanical forces
occurring during grinding and rolling. On account of the initiation way, the degrada-
tion processes caused by physical factors can be divided into thermal, mechanical,
and photochemical degradation [21, 22].
The thermal degradation is caused by a temperature. In the majority of cases,
polymers are thermally stable up to a temperature of approximately 200 °C. At a
temperature of approximately 1000 °C, they disintegrate into small fragments of the
type of free radicals, free ions and H2, CO, CO2, etc. The thermal sensitivity of
organic substances is caused by covalent bonds. Two phenomena are effects of
chemical changes occurring when polymers are heated: chemical bonds C–C in the
main chain or in side chains are ruptured, which is revealed by decreasing of a molar
mass and low-molecular gaseous products are emitted.
Curves of the thermal disintegration of the most important multimolecular sub-
stances are presented below (Fig. 2.12). It is seen from these curves positions that
the thermal degradation of the majority of polymers starts already at temperatures
150–200 °C and ends below 400 °C, with the exception of thermally stable phenolic
polyester and urea resins. Disintegration of these resins ends only at temperatures
600–800 °C, in addition to which a high content of coke in pyrolysis products is
characteristic. The pyrolysis course of polyvinylchloride is interesting. The process
of the hydrogen chloride 100% removal from PVC occurs at a temperature below
Fig. 2.12 Curves of the thermal decomposition of selected polymers (PP, polypropylene; PE,
polyethylene; PS, polystyrene; PVC, polyvinylchloride) [16]
200 °C, and in the case of mixtures containing PVC, the process of hydrogen chlo-
ride emission can precede the relevant pyrolysis. Some polymers, e.g., polymethyl
methacrylate or polystyrene, undergo depolymerization during heating. Then it is
possible to recover – at least partially – the monomer [23].
The characteristic product of burning polymers, based on organic aromatic sub-
stances, especially polystyrene, is soot. It was found that amounts of soot can be
limited when the polystyrene burning process is carried out in weakly oxidizing
atmosphere. In dependence on the amount of oxygen, the soot oxidation to CO and
CO2 occurs. During burning of polymers containing nitrogen atoms in macromole-
cules, e.g., polyamides, polyurethanes characteristic of yellow fumes formed by
nitrogen oxides, the so-called NOx, are emitted. A serious threat to the life consti-
tutes hydrogen cyanide (HCN) formed at burning of polyacrylonitrile.
Generally the majority of macromolecular substances undergo unordered
destruction during pyrolysis, usually with emitting volatile substances of small
molecular masses, such as aliphatic hydrocarbons of various chain lengths, aro-
matic hydrocarbons, carbon oxide and dioxide, hydrogen chloride, water, and
hydrogen. In dependence of the supplied oxygen and process temperature, coke can
be obtained as a solid residue.
The mechanical degradation concerns macroscopic effects occurring in poly-
mers under the influence of tensile forces.
The photochemical degradation occurs under an influence of visible light or
ultraviolet and leads to physical and chemical changes of polymer. The photochemi-
cal degradation is especially essential from practical reasons. Plastic products being
in general use are usually exposed to sunlight. This light contains a wide radiation
range, including visible and ultraviolet ranges, causing disadvantageous changes of
polymer properties.
Factors causing the chemical degradation are mainly oxygen and ozone.
Molecular oxygen, present in the air, facilitates the degradation process of polymers
at relatively low temperatures, already at a room temperature. Even more easily this
reaction proceeds under an influence of atomic oxygen or ozone. The reaction of
ozone or oxygen with the polymer containing a double bond, in which the polymer
is degraded into aldehydes and acids, is applied for producing degradable polymers.
Plastics obtained in such a way are degrading under natural conditions and can be
utilized after being used. This process can proceed also under an influence of acids,
bases, or corrosive agents.
The biodegradation process proceeds under an influence of biological agents:
bacteria, enzymes, and fungi. This process is based on the disintegration of plastics,
after a determined time and after finishing its usage. All natural macromolecular
products, even wood and ivory, can be degrading to small particles; when producing
them, organisms die. A composition and character of disintegrating substances
allows for using them by other organisms in order to produce energy or for synthesis
of new substances, including also biopolymers. In exceptional cases, natural bio-
degradation processes are leading to forming such final products as coal, peat, and
hydrocarbons, which can be considered to be completely degraded biopolymers
[16, 24]. The biodegradation process can be anaerobic, progressing without the air
access – less efficient and less common in nature, leading to formation of methane
and other simple hydrocarbons – or aerobic at the air access. The final products of
aerobic biodegradation are carbon dioxide and water, sometimes mineral salts. In
between individual degradation types, there are strong connections. Usually a few
types occur simultaneously. Simultaneous operations of light, oxygen, and other
atmospheric agents or simultaneous operations of heat, mechanical forces, and oxy-
gen are typical examples of such situations.
2.5.6 Natural Polymers (Biopolymers)
Biopolymers are macromolecular substances produced by organisms. They can be

divided into groups [15]:
• Nucleic acids.
• Peptides, proteins.
• Polysaccharides (cellulose, starch, collagen, chitin, and chitosan).
• Natural rubbers.
Examples of Natural Polymers
Cellulose
Cellulose (fiber) is a natural polymer, from the polysaccharide group, produced
by photosynthesis. Cellulose constitutes the basic component of plants, which pro-
vides elasticity and stability to cell walls and protects against water losses. This
polysaccharide is built of D-glucose mers, connected by β-glycoside bonds at car-
bon atoms: C1 and C4. Each heterocyclic ring of cellulose contains:
• One primary alcoholic group (–CH2OH).

• Two secondary alcoholic groups (–OH).
CH2OH CH2OH CH2OH CH2OH

O O O O OH
H H H H
H H H H
O
O OH H OH H
OH H OH H H
H H
HO
H OH H OH H OH H OH
n
cellulose formula (n approx. 2000)
The average polymerization degree of cellulose equals 500–10,000.

The natural raw material containing the highest amount of cellulose is cotton,
followed by linen and hemp. Cellulose, regardless of a large number of hydroxyl
(–OH) groups, does not dissolve in water and organic solvents. Cellulose is swelling
in water due to forming hydrogen bonds with free hydroxyl groups; it dissolves in
HCl, H2SO4, HF, tin chloride, and bismuth chloride. Cellulose is anisotropic poly-
mer and durability of fibers is ten times higher along the fiber axis than in the trans-
verse direction.
Starch
Starch is a natural biopolymer from the polysaccharide group. It constitutes a
mixture of two kinds of polyglucans [25]:
• Amylose of an average polymerization degree: P = 5000.
• Amylopectin of an average polymerization degree: P = 50 000.
Typical starch contains 20–30% of amylose. Starch has a globular structure and
occurs in plants in a form of grains of sizes: 0.2–100 μm. Starch is produced by
plants in the process of carbon oxide assimilation, (IV) CO2. It is deposited in cells,
as the so-called reserve material. Thus, the following process occurs in plants (glu-
cose under an influence of enzymes is turning into starch):
hv
CO2, H2O glucose, oxygen
chlorophyl
enzyme
starch
Water solubility of starch depends on a temperature. It does not solve in cold

water, while strongly bulge in hot water: 95–85 °C [19]. By substituting a part of
hydroxyl groups by ester or ether group, the modified starch is obtained.
The most important starch property is its ability to hydrolysis. Hydrogen ions
and enzymes, called amylase, are catalysts of the starch hydrolyses. The scheme of
the hydrolysis reaction is as follows (Eq. 2.67):
HCl HCl

( C6 H10 O5 )n + nH 2 O → ( C6 H10 O5 )x → C12 H 22 O11 → n ( C6 H12 O6 )

starch hydrolysis x < 10 maltose hydrolysis glucose

dextrin
( C6 H10 O5 )n → ( C6 H10 O5 )n → C12 H 23 O11 → C6 H12 O6

(2.67)
starch dextrin maltose glucose
A majority of currently produced biodegradable plastics are mixtures containing

starch, modified starch, and cellulose and also synthetic polymers – modified by
starch – as fillers.
Modified Starch
Modified starch is produced of natural starch by means of physical, enzymatic, or
chemical changes. Due to these processes, its various applications, not only in the
food industry, are possible. Starch modifications allow to provide it with new fea-
tures and improvements of functional properties. Starch can be subjected to three
kinds of modifications, which allow its more efficient application in industry and
achieving better properties of final products [26].
Physical modifications – natural starch is subjected to heating at high temperatures,
preliminary gelation, and then drying on drying rollers. During this process the
starch crystalline structure decays.
Enzyme modifications – in their results the starch hydrolysis, i.e., disintegration into
substances of lower molar masses, occurs.
Chemical modifications – during chemical modifications hydroxyl groups (-OH)
present in starch are substituted by other chemical substituents. Starch is modi-
fied in reactions of oxidation, esterification, and etherification.
Modified starches are significantly different than natural starch. Rheological
properties obtained in the starch modification processes, applied widely in the
industry, are:
• Binding of large amounts of water together with substances dissolved in it.
• Wide viscosity range.
• Variable gelatinization temperatures (from a room temperature to above 100 °C).
• formation of various gels,

• Resistance to retrogradation process (precipitation of starch particles from the
formed structure).
• Clarity and transparency of gluels and gels.
• Absorption of various substances, e.g., tasty, smelling, alcohols.
• Ability to stabilize emulsions and suspensions.
• Ability to forming flexible films.
Poly(Lactic Acid) (PLA)
Poly(lactic acid) (PLA) is fully biodegradable aliphatic linear polymer, obtained
from lactic acid (2-hydroxypropionic) constructed of macromolecules, built of
basic units of the same polyester chemical structure.
Lactic acid is a weak water-soluble organic acid, which is obtainable either
chemically or in milk fermentation of carbohydrates (e.g., starch) caused by bacte-
ria. PLA is a thermoplastic polymer of a melting temperature of 180 °C. PLA is
dually applicable: in medical aims and as thermoplastic materials produced of
renewable raw materials, able for self-degradation (its final degradation products
are CO2 and H2O). Lactic acid is produced on the industrial scale mainly of carbo-
hydrates of the agricultural origin (potatoes, corn, sugar beet, biomass) [26].
Natural Resins
Natural resins are produced in biochemical processes by life organisms, the most
often by vegetables. There are organic substances containing esters, alcohols, car-
boxylic acids, and other organic compounds. To natural resins belong, among oth-
ers, amber and colophony [26, 27].
Amber is a fossil resin, which was created from extinct coniferous trees. In its
composition are polyesters of succinic acid (more than 70%). Amber, after being
melted, undergoes a partial thermal destruction and dissolves in aromatic hydrocar-
bons in petrol and turpentine.
Colophony is obtained from coniferous trees, the most often pines. This is a mix-
ture of rosin acids, which contain carboxylic groups and unsaturated bonds.
Colophony softens at temperatures 68–75 °C while above 200 °C undergoes
decarboxylation.
Natural Rubber
Natural rubber is the only natural polymer, of which – during pyrolysis – monomer
is obtained. It is obtained from the special tree and plant species, as a latex compo-
nent, rubber-wood juice, where it constitutes approximately 30%. Its main applica-
tion is the rubber production in the vulcanization process, during which a partial
cross-linking of rubber macromolecules occurs. The rubber vulcanization process is
performed with additions of 1.5–2% of pulverized sulfur and heating such mixture
at temperatures 130–150 °C [15].
References
1. Meyer T, Keurentjes J (eds) (2005) Handbook of polymer reaction engineering. Wiley,

New York
2. Majewski W (2012) Mechanisms of organic reactions. UMSC, Lublin. (in Polish)
3. Clayden J, Greeves N, Warren S (2012) Organic chemistry. Oxford University Press,
Oxford, U.K
4. Klein D (2011) Organic chemistry. John Wiley & Sons, Hoboken
5. McMurry J (2010) Fundamentals of organic chemistry. Cornell University, Belmont, USA
6. Ouellette RJ, Rawn JD (2014) Organic chemistry: structure, mechanism, and synthesis.
Elsevier, San Diego
7. Stasicka Z, Achmatowicz O (eds) (2005) International union of pure and applied chemistry.
Compendium of Chemical Terminology of the Polish Chemical Society, Cracow. (in Polish)
8. Zakaria A, Noweir K, El-Maghrabi G (2005) Evaluation of occupational hazards in foundries.
J Egypt Public Heal Assoc 80:25–31
9. Carey F, Sunfberg RJ (2007) Advanced organic chemistry. Springer Nature Switzerland AG
10. Clarke HT (2015) An introduction to the study of organic chemistry. Andesite Press
11. Nechamkin H, Meislich H, Sharefkin J, Hamemenos GJ (1999) Theory and problems of
organic chemistry. McGraw-Hill, USA
12. Tadmor Z, Gogos CG (2006) Principles of polymer processing, 2nd edn. John Wiley &
Sons, USA
13. Rabek JF (2013) Polymers obtaining, research methods, applications. PWN, Warsaw.

(in Polish)
14. Dutta PK (2016) Natural polymers. Springer, Berlin
15. Rabek JF (2017) Modern knowledge of polymers. PWN, Warsaw. in Polish
16. Wilczura-Wachnik H. Combustion and thermal degradation of polymers. An outline for labo-
ratory exercises. Accessed 14 Jun 2019 (in Polish)
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Publishing House. (in Polish)
18. Kilarska J, Solarski W, Zawada J, Zieliński E (1990) Chemistry of binders for molding and
core sands. Publishing House AGH, Cracow. (in Polish)
19. Pielichowski J, Puszyński A (2012) Polymer chemistry. Educational Society FOSZE. (in
Polish) Rzeszów, Poland
20. Pillai CKS (2014) Recent advances in biodegradable polymeric materials. Mater Sci Technol
30:558–566
21. Pielichowski K, Njuguna J (2005) Thermal degradation of polymeric materials. Rapa

Technology Limited, Crewe, UK
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posites. Springer, Berlin
23. Banerjee A, Chatterjee K, Madras G (2014) Enzymatic degradation of polymers: a brief
review. Mater Sci Technol 30:567–573
24. Schnabel W (1981) Polymer degradation. Akademie-Verlag, Berlin
25. Visakh PM, Yu L (eds) (2016) Starch-based blends, composites and nanocomposites. Royal
Society of Chemistry, Cambridge
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ites and nanocomposites. Springer - Verlag Berlin, Germany.
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Phenolic resins (IV). Thermal degradation of crosslinked resins in controlled atmospheres.
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Chapter 3
Synthetic Resins
3.1 Alkyd Resins
Alkyd resins1 – products of the polyester resins modifications caused by oils, mainly
vegetable oils. Polyester resins are products of polycondensation of polyhydric
alcohols with polycarboxylic acids. Alkyd resins are formed by the polycondensa-
tion reaction of phthalic acid anhydride, glycerine, and vegetable oils (vegetable oil
is subjected to transesterification process) with the presence of catalysts in solution.
In dependence on the length, polymerization method, and used components (first of
all, the vegetable oil kind), they obtain various features and properties. Alkyd resins
belong to the group of polyester thermoplastic resins [1, 2].
Taking into consideration the character of fatty acids or vegetable oils contained
in alkyd resins, they can be divided into two main groups:
• Alkyd resins drying at a room temperature
• Alkyd resins not drying at a room temperature
To the first group belong resins modified by vegetable oils or fatty acids contain-
ing double bonds in the coupled or isolated system. They have the ability of forming
lacquer coatings under an influence of oxygen from the air. In order to accelerate the
hardening process, salts of cobalt, manganese, or calcium are added as catalysts.
Cobalt salts are the most efficient but since they are toxic, they are usually substi-
tuted by less harmful ones. Lately, the laccase enzyme produced, among others, by
fungi growing on wood, is proposed as a catalyst. This natural substance in combi-
nation with the adequate mediator can catalyze the cross-linking of alkyd resins
equally well, as presently applied substances. To the second group belong resins
modified either by saturated fatty acids or by acids containing only one double
1
Name alkyd originates from alkyl (chemical shortening of alcohol) and word acid, determining
chemical origin of resin, which the most often is the product of the polymerization reaction in
between alcohol, such as glycerol, and dicarboxylic acid or its anhydride.

84 3 Synthetic Resins
Fig. 3.1 Polymerization of alkyd resin with using phthalic acid anhydride, glycerine, and fatty
acid
bond. They are forming lacquer coatings as a result of chemical reactions with
amine resins or are used as plasticizers of other film-forming substances [1, 3, 4]
(Fig. 3.1).
Apart from basic substances, alkyd resins contain one more chemically intro-
duced component. This modification is aimed at improving the needed properties of
alkyd resins. Unfortunately, worsening of some other properties is related to that, as
modifying components are used: resins, styrene, vinyl, toluene, acryl, epoxides,
isocyanine, silicones, and amines [1].
Alkyd resins are relatively cheap, stable, elastic, and temperature resistant.
Typical structure of alkyd resin is shown below:
where R represents long chain of alkyl (CnH2n+1) group, characteristic for fatty acids
[1, 3, 5].
3.2 Phenol–Formaldehyde Resins
Phenol
Phenol (C6H5OH) (another name hydroxybenzene) is the simplest substance from
the phenol group, to which belong cresols and xylenols. This is a group of aromatic
3.2 Phenol–Formaldehyde Resins 85
Table 3.1 Properties of phenol [6]

Parameter
CAS no. 108-95-2
Molecular weight 94.1
Melting point 40.9 °C
Boiling point 181.8 °C
Flash point 79.0 °C
Auto-ignition 605 °C
Explosive limit 2–10%
Vapor pressure at 20 °C 20 Pa
MAK limita 19 mg/m3/5 ppm
OSHA PELb TWAc 5 ppm
a
MAK limit is the maximal concentration of chemical substances (gas, vapors, or solid particles)
at the workplace, for which it is not known whether it is negatively influencing employees health
or creates unfavorable work conditions (e.g., unpleasant smell) even when the person is exposed
several times
b
OSHA PEL (the permissible exposure limit) is the permissible concentration of chemical sub-
stances or intensity of physical agents, e.g., loud noise (US) for 8-hour work day
c
TWA – a time – weighted average is the average exposure in the given time, usually 8 hours
compounds, in which hydroxyl (−OH) group is directly connected with the aro-
matic ring. The main method of obtaining phenol is the cumene process. Another
method is based on the reaction of oxidizing toluene, in the presence of a cobalt
catalyst, to benzoic acid which is then subjected to decarboxylation in the presence
of a copper catalyst. At a room temperature, phenol is colorless crystalline solid. Its
melting temperature equals 40.9 °C, while the boiling point is 182 °C. After melting
phenol is colorless liquid. Even traces of water are decreasing the phenol melting
temperature by app. 0.4 °C for each 0.1% of water. Phenol dissolves in aromatic
hydrocarbons, alcohols, ketones, ethers, and acids. It dissolves worse in aliphatic
hydrocarbons and moderate in water. The basic properties of phenol are listed in
Table 3.1.
Due to the presence of hydroxyl group and aromatic chain, phenol has specific
chemical properties. It has weak acidic and weak basic properties. It reacts with
formaldehyde and in dependence on the environment pH forms resins either of the
novolak type (in acidic environment) or the resol type (in basic environment).
Phenol is a toxic compound. It destroys mucous membranes and airways. It can
lead to laryngeal and pulmonary edema and to necrosis of oral cavity and digestive
tracts. In a similar fashion as other harmful substances available in households,
phenol is sometimes the reason of poisoning and burns.
Formaldehyde
Formaldehyde (methanal, formic aldehyde) (HCHO or CH2O) under normal condi-
tions is a colorless gas of suffocating smell. It is a strong poison. It can be obtained
by two methods: either by catalytic oxidation of methanol in a gas phase, above iron
and molybdenum oxide, or by using silver at temperatures 300–600 °C.
Table 3.2 Properties of Parameter

formaldehyde [6]
CAS no. 50-00-0
Molecular weight 30
Melting point −92 °C
Boiling point −19 °C
Flash point 60 °C
Auto-ignition >300 °C
Explosive limit 7%
MAK limit 0.5 ppm
OSHA STEL 2 ppm
This is the first aldehyde from the group of aliphatic aldehydes. Its melting
temperature equals −92 °C while a boiling point −19.1 °C (Table 3.2).
Formaldehyde is well soluble in ethanol, chloroform, and water. Formaldehyde is
a very reactive substance, since the carbonyl group in its particle has no carbon
substitutes, and due to that the carbon atom in this group easily condensates.
Therefore formaldehyde very easily forms polyoxymethylene (paraformaldehyde)
in polycondensation reaction. Aqueous solutions of formaldehyde, which are
applied in the resin production, are unstable especially at low temperatures and
indicate a growing tendency to precipitating of paraformaldehyde. Therefore
commercial grades of this substance are stabilized by various amounts of methyl
alcohol (up to 15%).
Formaldehyde belongs to the group of dangerous chemical substances and is
classified as the proven carcinogenic for humans. Formaldehyde is easily absorbed
into organisms by airways. It irritates conjunctivas and mucous membranes. It has
an acute and chronic toxic activity. A connection between an exposure to formalde-
hyde and leukemia morbidity is also noticed [7, 8].
Methylene Glycol
This substance is formed in a reaction of formaldehyde with water. Since this reac-
tion is reversible, products containing methylene glycol can – under certain condi-
tions – release formaldehyde. Both substances occur in equilibrium and under
various conditions easily change one into the other. The changing rate depends on a
temperature, pH, concentration, and presence of other substances.
Phenol–Formaldehyde Resins
Phenol resins are one of the oldest resins commercially produced by means of
polymerization. The first information concerning them provided Von Baeyer in the
year 1872. The first patent concerning producing phenol–formaldehyde resins dates
back the year 1907 and belongs to Leo H. Baekeland.
Phenol resins are thermo-hardened polymers of a high resistance to chemical

agents, but of a low resistance to dynamic loads and mechanical operations. Phenol
resins are resistant to self-ignition; they generate small amounts of fumes and are
relatively cheap. In order to improve thermal properties of phenol resins, phenol–
formaldehyde resins are applied [9].
Phenol–formaldehyde resins (phenoplasts) belong to the group of condensation
resins, widely applied in the industry. They are used, among others, for a production
of friction and abrasive materials, coatings of molds and cores for the foundry
industry, electro-insulating products, thermo-insulating products, products of min-
eral wool and glass fibers, laminar plastics, binders applied in furniture industry,
glues, paints, and products of general use [8].
Phenol–formaldehyde resins are synthetic thermo-hardened polymers resulting
in the polycondensation reaction of phenols with aldehydes, usually with formalde-
hyde. Water is the by-product of this reaction. Since this reaction without a catalyst
is very slow, the catalyst is always added. It can be either acid or base. These resins
are solvable in organic solvents and can be melted.
The kind of the product depends on the catalyst and molar ratio of reagents.
Polymerization of Phenol and Formaldehyde
Phenol and formaldehyde are raw materials for production of phenol–formaldehyde
resins for the needs of the foundry industry. In aqueous solution, formaldehyde is in
equilibrium with methylene glycol (CAS 463-57-0) (hydrated formaldehyde):
The polycondensation reaction of phenol with formaldehyde is catalyzed by

hydrogen ions as well as by hydroxyl ions. This process can be carried out in an
aqueous solution. Phenol with formaldehyde reaction is highly exothermic [10, 11].
Depending on the environment pH, in which this reaction occurs, and on the
mutual fraction of each reagent (phenol and formaldehyde), one of two types of
resins are obtained: novolak resin (in acidic environment, at phenol surplus) or resol
resin (in basic environment, at formaldehyde surplus) (Fig. 3.2). Since novolak
resin does not contain reactive groups, it requires an additional cross-linking agent
and heat in order of hardening [10, 12–16].
The polymerization reaction course of both kinds of phenol resins can be written
as (Fig. 3.3):
The phenol polymer formed in polymerizations of resol and novolak resins is the
same. The only difference constitutes the fact that the polymer obtained from resol
resin does not contain hexamethylenetetramine, which can release nitrogen or
ammonia.
In the first stage of the polycondensation of phenol with formaldehyde, the elec-
trophilic connection of the formaldehyde particle into phenol group in ortho- or
para- position occurs with a simultaneous rearrangement of the hydrogen atom with
oxygen atom (Fig. 3.4) [17, 18].
OH OH
CH2
CH2OH
base
F/P 1
OH
CH2 CH2OH
O
+ CH2O resol resin
CH2
OH
CH2OH
OH OH
acid
CH2
F/P 1
novolak resin
OH
Fig. 3.2 Scheme representing polycondensation of phenol and formaldehyde to obtain various
products of this reaction, depending on the reaction conditions. (Reprinted by permission from
Ref. [12])
Fig. 3.3 Schematic presentation of the polymerization process course of novolak and resol phenol
resins
Fig. 3.4 Scheme of the

phenol and formaldehyde
connection
Hydroxymethyl (−CH2OH) group can be connected in the position ortho- or

para- into OH- group in the phenol particle. Then mono-, two-, and tri-hydroxyphenol
derivatives are formed (Fig. 3.5).
These derivatives are condensed, and in result oligomers with methylene –CH2−
bonds are formed, and formaldehyde is evolved (Fig. 3.6).
The obtained substances can react with each other via hydroxymethylene groups,
connecting themselves by the ether –CH2−O−CH2− bond (Fig. 3.7).
Reactions of this type are further occurring providing in result phenol–formalde-
hyde resin.
Fig. 3.5 Scheme of the formation of hydroxyl derivatives in the reaction of phenol with
formaldehyde
Fig. 3.6 Condensation of hydroxyl derivatives
Fig. 3.7 Formation of the ether bond as the result of condensation of hydroxyl derivatives
Novolak Resins
In the acidic environment (pH = 4–7), the initial reaction between methylene glycol
and phenol (at a small surplus of phenol) is as follows:
OH OH OH
H CH2 OH2
HO CH2 OH and H2O
CH2 OH2
methylene glycol phenol methylphenol
(0.8 M) (1M) pH < 5 ; 95 oC
+ OH OH OH ortho-ortho
CH2 OH2
CH2
and + + H2O + H+
OH
+
CH2 OH2 and
OH ortho-para
CH2
+ H2O + H+
OH
and
para-para
CH2
+ H2O + H+
OH OH
Fig. 3.8 Possibility of forming methylene bridge (−CH2−) in ortho- or para- position aromatic
ring. (Adapted from Ref. [19])
This reaction produces methyl phenols, which are very active in an acidic
environment and react very fast with free phenol (Fig. 3.8).
As the reaction result the methylene bridge (−CH2−) is formed in the ortho- or
para- position of the aromatic ring of phenol. The para- position is nearly twice
more reactive than ortho-, but there are twice more positions ortho- (two in the phe-
nol particle), and in consequence fractions of bridges ortho–ortho, para–para, and
ortho–para are, in approximation, the same [19].
Further branching occurs since the reaction can take place in three places of each
ring. This reaction stops, when formaldehyde is exhausted and that time often
remains app. 10% of not reacted phenol (this is the so-called free phenol).
Since novolak resin contains only methylene (−CH2−) groups but does not con-
tain free reactive hydroxymethylene (−CH2−OH) groups, heating of this resin – as
the only factor – does not cause further reactions and cross-linking. Thermoplastic
resin of a linear structure and not cross-linked is obtained. This resin cannot be fur-
ther hardened without an additional cross-linking agent. Therefore novolak resins
are called two-stage resins. It is necessary to supply the system with an additional
portion of formaldehyde. Hexamethylenetetramine, known as HMTA or hexamine
(Fig. 3.9), can be the cross-linking factor. This substance, at a temperature of 160 °C,
decomposes into ammonia and formaldehyde.
OH
OH
N H2 C
CH2 N
HN H2 C
N N CH2 OH
N
CH2
HO
OH
Fig. 3.9 Formula of hexamethylenetetramine and the structure of cross-linked novolak resin (for-
mation of methyleneamine bridges). The hardening process occurs in two stages

( CH 2 )6 N 4 + 6H 2 O = 6CH 2 O + 4NH3
Novolak resin + HMTA + heat → cross − linked polymer + H 2 O

HMTA hardens resins by means of further cross-linking and polymerization of
particles, up to the state of a high melting temperature (methyleneamine bridges are
formed) (Fig. 3.9). However, the only presence of HMTA does not cause the resin
hardening. Heating of the system is necessary. Hardening by means of HMTA is
based on reactions, at a temperature above 150 °C, of active places (free ortho- or
para- positions in a chain) with partially decomposing HMTA, according to the
scheme (Fig. 3.10) [20]:
HMTA dissolves relatively well in water while weaker in methanol or ethanol. It
easily hydrolyzes into amino methyl substance. Its aqueous solution has weak basic
properties of pH = 7–10.
Novolak resin is a solid thermoplastic material of properties not changing with
time. As it is shown by the newest studies [20, 21], novolak resins during their stor-
age indicate only negligible changes in chemical composition, caused mainly by a
partial hardening. Hardened resins also indicate only small changes with time.
Novolak resins are amorphous (they do not crystallize) and thermoplastic. At a
room temperature they are solids, which soften and flow at temperatures between 65
and 105 °C. These resins are soluble in several organic, polar solvents (e.g., alco-
hols, acetone), but insoluble in water and aromatic hydrocarbons. At heating,
novolak resins are melting but are not condensing further (because they do not con-
tain reactive hydroxymethyl (−CH2OH) groups). Generally, at temperatures up to
250 °C, novolaks are not chemically changing.
Resol Resins
Resol resins are obtained in the basic environment and at a surplus of formaldehyde
over phenol (the most often: formaldehyde/phenol = 1.5:1 and 2.5:1). Industrial
Fig. 3.10 Cross-linking of novolak resin in the hexamine presence. (Reprinted by permission
from Ref. [20])
synthesis of resol resins is often carried out in the presence of catalysts based on
ammonia or tertiary amine, or NaOH [22, 23]. Advantages of resol resins, produced
in the presence of trialkyl-amines, are longer gelling time, smaller amount of ashes,
and resistant to hydrolysis. An addition of urea in the final production stage of the
resol-type resin improves its viscosity and decreases production costs. Resol resins,
contrary to novolak resins, have unreacted hydroxymethylene (−CH2OH) groups,
and phenol particles are connected by methylene (−CH2−) bridges, as well as by
dimethylene ether (−CH2−O−CH2−) bridges.
The polycondensation process of phenol and formaldehyde can be presented as
follows.
Phenol reacts with methylene glycol forming hydroxymethylphenol (phenol
with one or a few hydroxymethylene (−CH2OH) groups), when indirectly phenyl–
alcohol is formed (reaction of electrophilic joining of aldehyde):
At a temperature above 110 °C, methylene glycol totally dissociates into

formaldehyde and water. Methyl phenol molecules react with each other via
hydroxymethylene groups, either connecting themselves by dimethylenether
−CH2−O−CH2− bond:
or methylophenol particles are reacting with phenol particle, connecting themselves

by methylene −CH2− bond:
In benzene ring positions, marked X, there is still a possibility of reaction.

In case of resol resins, where is a surplus of formaldehyde, there is a sufficient
amount of reactive hydroxymethylene (−HO−CH2−) and dimethylene ether (−
CH2−O−CH2−) groups to complete the polymerization, without introducing a
hardening addition, and providing in effect phenol–formaldehyde resin (Fig. 3.11).
Therefore resol resins are called one-stage resins. By controlling the phenol
amount ratio to the formaldehyde amounts, pH, temperature, catalyst kind, and
reaction time, it is possible to obtain resins of various properties [17].
The polymerization reaction of resol resin occurs even at a room temperature,
however much slower. The typical average number of molecular mass units in nor-
mal resol resin equals from 200 to 450.
The cross-linking degree of resin decides on its properties, such as temperature
of softening under load, stiffness, etc. Phenol–formaldehyde resol resins are liquid
or solid thermo-reactive products, which color – yellow or red – depends on the
applied catalyst. Liquid resol resins have on average app. two benzene rings in a
molecule while solid resol resins three to four rings. Resol resins are to a certain
degree water soluble, while they are well soluble in alcohols and acetone. However,
after hardening they are completely losing their solubility.
During storing resol resins are changing into the infusible and insoluble state.
Heating is accelerating this process. In a temperature of 150 °C the hardening
time equals app. 50 s. Organic and inorganic substances can be applied as cata-
lysts of hardening phenol–formaldehyde resins. Resol-type resins hardened in the
OH OH OH OH OH
H CH2 CH2 CH2 CH2 CH2 CH2OH
C O
C
CH2OH CH2 H CH2 CH2
O
OH CH2 OH
HOCH2 CH2OH
CH2 OH
OH CH2
CH2
CH2 CH2
HO O
C
CH2OH
H
Fig. 3.11 Structure of cross-linked phenol–formaldehyde resol resin

presence of organic catalysts are characterized by a high resistance to humidity

and high mechanical strength [24, 25].
Some resols contain latent acid catalysts (which are becoming active, e.g., after
heating), which generate moderately strong acids [6]. This can be, e.g., (NH4)2SO4
or biphenyl hydrogen phosphite. The application of latent catalysts allows to widen
the resin utilization range – since it prolongs its liquidity time.
Several additions are applied in the production process of PF resol-type resins.
These additions are introduced in order to extend the storage time, widen appli-
cability, or control the hardening rate. The urea addition in the final phase of the
resol resin synthesis is a usual practice [26]. It not only reduces costs of resins
but also decreases their viscosity and thus influences their other properties. The
application of tertiary amines R3N as catalysts extends a gelling time, decreases
ashes amounts, and improves a resistance to hydrolysis [22]. Methanol is usually
added at the beginning of the synthesis to control the heat effect of the polymer-
ization process. At pH 4–6 the hardening process of phenol–formaldehyde resol-
type resin is slower than at pH 8 and higher, but significantly slower than
at pH 1–3.
Important differences between phenol–formaldehyde resins of novolak and
resol type:
• Resol resins are produced with basic catalyst while novolak resins with acidic
catalyst.
• Resol resins have hydroxymethyl HO−CH2− groups, while novolak resins do
not have these groups.
• Resol resins have a short storage time, while novolak resins can be stored for a
very long time.
• Resol resins release water during hardening, while novolak resins release ammo-
nia (by decomposition of hexamine, a binder component).
• Novolak resins are characterized by more than twice better dimensional stability
than resol resins.
• Resol resins are usually liquids, while novolak resins are solids.
PF resins are characterized by a high resistance to creep and to deformations
under loads, by a low thermal conduction and are good insulators. They are resistant
to chemical agents (resistant to influences of weak acids, weak bases, hydrocarbons,
and detergents), have low tendency for water absorption (from 0.03% to 1.75% –
resol resins are more humidity resistant), and have high dimensional accuracy and
stability [27].
Water in a powder resol resin plays an important part in the curing. In the initial
curing stages, water acts as diluent and retards the curing. At the higher conversion,
water acts as plasticizer.
Phenol–formaldehyde resins, both novolak and resol type as well as their mix-
tures with other resins: phenol/polyurethane and phenol/urea resins are widely
applied in the foundry industry as components of binders for molding and core sands.
Processes of productions of molds and cores are listed in Table 3.3.
Table 3.3 Processes of molds and cores production in which phenol–formaldehyde resin is used
Phenolic resin Hardener/catalyst Process
Novolak Hexa (HMTA) Croning process
Resol Acid + heat Hot-box process
Resol Polyisocyanate/amine Polyurethane cold-box process
Resol Liquide ester ALPHASET process
Gas ester (methylformate) MF: cold-box process BETASET
Carbon dioxide CO2 – resole process
Reprinted by permission from Ref. [12]
Harmfulness of Phenol–Formaldehyde Resins

The reaction of phenol with formaldehyde is highly exothermic [28]. During pro-
cessing of resins, these substances are hardened due to a high temperature influence
(from 160 to 250 °C). In this process the mixtures of harmful substances of various
chemical character and various toxicity degrees are released into the atmosphere at
workplaces. The source of these substances are resins themselves, substances modi-
fying their properties, and certain additions. An exposure of employees to chemical
substances can occur also during the preparation of mixtures and forming products
since that time resins are being cross-linked. Phenol and formaldehyde are in a free
state in not hardened resin. Qualitative and quantitative composition of emitted
harmful substances depends on the resin kind and on conditions under which the
hardening occurs, i.e., temperature, pressure, and time of their operations, as well as
on the surface of produced elements.
Hexamine added to novolak resins can be decomposing and emitting ammonia,
under conditions of hardening. On the other hand, formalin (saturated aqueous solu-
tion of formaldehyde) applied as a raw material for the production of phenol–form-
aldehyde resins can be the source of the methanol presence in the air on the
workplaces; 12% of this alcohol is added into formalin as a stabilizer [29, 30].
A problem is the release of phenol into the atmosphere during curing. Typical
levels of free phenol in the phenol–formaldehyde resin are in the range of 5–15%.
One method of reducing the free phenol level in the base phenol–formaldehyde
resin is to increase the amount of formaldehyde in the resin during manufacturing.
Thermal Degradation
Thermostability of thermo-hardened polymer to a significant degree depends on its
structure and cross-linking density. The polymer stability is an important property.
The thermal degradation of phenol–formaldehyde resin starts from cracking of
bonds between aromatic rings and methyl (−CH2−) bridges (Fig. 3.12) [31]. When
hydrogen atoms are connecting with the formed radicals, phenol and its derivatives
are created. Products formed during the thermal degradation of phenol–formalde-
hyde resin are forming compounds of condensed aromatic rings, e.g., fluorine
[32, 33].
Investigations concerning the mechanism of the thermal degradation of PF res-
ins [34–36] suggest that their thermal decomposition occurs according to the autox-
idation process, which combines three stages [24–26]. Moreover, at considering the
OH OH OH OH OH
CH2 CH
+ + H2O
OH OH OH OH
CH2 CH2
2 2 + 2
OH OH
CH2 CH2
2
Fig. 3.12 Possible reactions occurring at the thermal degradation of PF resin. (Adapted from Ref.
[31])
PF resin pyrolysis, two ways of heating should be taken into account, which will
simulate effects occurring in a mold: “slow” and “flash.” The “flash” pyrolysis
takes place in the initial period during a mold pouring with molten metal, while
“slow” pyrolysis occurs in molding sand layers being at a significant distance from
a casting. The heating method and character of the atmosphere, in which the pro-
cess occurs, have the influence on the kind and amount of evolving substances. In
case of “slow” pyrolysis, the thermal destruction of PF resin runs in three
main stages.
In the first stage, the additional cross-linking between remained unreacted func-
tional groups in hardened PF resin occurs. Along with a temperature increase from
a room temperature to 200 °C, the resin mass loss is mainly caused by releasing
moisture, dehydration, as well as releasing substances of a low molecular weight.
Water releasing is a result of condensation reaction between the remaining hydroxy-
methyl −CH2OH and phenol −OH group. Water removal can lead to forming new
cross-linking [37, 38]. 5% of unreacted phenol can be in liquid resol resin while up
to <1% in liquid novolak resin. Free formaldehyde in resol resin can be in amount
<1%, while novolak resins are usually without formaldehyde.
In the second stage of the thermal decomposition, the cross-linking level is
reduced (further degradation proceeds). At a temperature range 200–400 °C the
mass loss occurs due to emission of free phenol, formaldehyde, short oligomers,
NH4+, CH4, and water.
In the third stage of the thermal degradation, cross-linking of hardened resin are
subsiding, and then carbonization and graphitization occur. When a temperature
3.3 Phenol–Urethane Binder System 97
increases to 400–600 °C, the main decomposition takes place. Mass losses are
caused by the polymer particles degradation and by formation of small and volatile
particles, such as CO, CO2, phenol, and benzoic aldehyde. At this temperature, the
formation of carbon (char) starts [6–8].
When a temperature grows above 600 °C, this degradation is continued, and
gradually the char like structure of carbon is formed, generating CO as a side prod-
uct. This can be considered to be the carbonization process [37, 39].
When the pyrolysis PF resin hardened by organic esters is carried out under
“flash” heating conditions, the products evolving to the environment (in dependence
on the pyrolysis temperature) are acetic acid, acetone, phenol, and its methyl deriva-
tives and eventual compounds containing nitrogen. When the pyrolysis temperature
increases to 700 °C benzene, its methylene derivatives are also emitting. At a tem-
perature of 1100 °C amounts of evolving phenol, benzene and toluene significantly
increases as compared with a temperature of 900 °C. Additionally, substances from
the PAH group of two rings are occurring [23, 37–40].
Phenol resins are characterized by larger amounts of “char” than other plastics,
when they are subjected to heating above their decomposition temperatures. In a
neutral atmosphere at high temperatures (300–1000 °C) phenol resins are trans-
forming into structural carbon known as vitreous carbon. In several cases this mate-
rial behaves in a similar fashion as a ceramic material [27, 29, 41, 42].
3.3 Phenol–Urethane Binder System
Urethane is a functional group, in which one carbon atom is connected with −OR
and −NR2 group. This [−O−CO−NH−] group is reactive. It means that urethanes
are intermediate between carbonate and urea; they contain:
Polyurethanes (PU) are formed as a result of the additive polymerization of

aromatic or aliphatic diisocyanates with substances containing at least two
hydroxyl −OH groups at chain ends (e.g., polyethers, polyesters). Polyesters con-
tain the ester (−O−CO−) bonds, while polyethers contain ether (−C−O−C−)
bonds in the main chain. The name polyurethanes originates from urethane groups
present in their structure. However, in fact, this name is a mental shortcut and can
be misleading, since these are not polymers of urethanes and even in a majority of
this type of polymers the urethane segment does not need to be the most important
Fig. 3.13 Polyurethane synthesis
part of a macroparticle. The urethane [−O−CO−NH−] group is formed in a reac-

tion of isocyanate (R−N=C=O) group with the hydroxyl groups of alcohol
(Fig. 3.13). In accordance with the polyaddition reaction mechanism, side prod-
ucts are not formed.
This reaction is a gradual process, which means that the molecular weight of
polymers, obtained by this method, systematically increases during successive
stages. This reaction is irreversible.
Phenolic urethane (PU) composed of a tri- part system which is made up of a
phenol–formaldehyde resin (Part I), MDI-type isocyanate (Part II), and amine cata-
lyst. Solvents are added to the Part I and Part II components to decrease the viscos-
ity and increase reactivity of binder. Amine, which is the catalyst can be in a liquid
form (phenolic–urethane no-bake process, PUNB) or in a gaseous form (phenolic–
urethane cold-box process, PUCB). Reaction of forming the urethane group [12,
43] can be written as follows (Fig. 3.14):
In dependence on the raw materials composition and reaction conditions, poly-
urethanes can contain polyethers or polyesters, in which at the chain ends hydroxyl
groups occur [12]. The most broadly applied is toluene −2,4-diisocyanate (TDI)
and 4,4′-diphenylmethane diisocyanate (MDI) (Fig. 3.15).
Polyurethanes are the group of polymers of comprehensive properties and the
widest variety of industrial applications. Polyurethanes are applied nearly in all
life and economy areas. Majority of polyurethanes are thermo-hardening poly-
mers, but thermoplastic polyurethanes also occur. Their drawback constitutes a
sensitivity to environmental factors, such as sun light (UV radiation) and acidic
environment. Foams are quantitatively the most important application of polyure-
thanes. Aromatic diisocyanates during hardening are changing color from yellow
to brown. This limits possibilities of their application. Aliphatic diisocyanates do
not have this disadvantage since they are colorless, but mechanical properties of
3.3 Phenol–Urethane Binder System 99
OH NCO O
catalyst
amine O C NH
+
phenolic polyisocyanate urethane bond

resin
−N = C = O + HO− = −O − CO − NH −
isocyanate urethane bond
Fig. 3.14 General equation of forming the urethane group. (Reprinted by permission from Ref.
[12])
CH3
NCO CH3
OCN NCO
NCO
toluene-2,4-diisocyanate (TDI) toluene-2,6-diisocyanate (TDI)
OCN CH2 N C O
(MDI)
diphenylmethane 4,4-diisocyanate
Fig. 3.15 Examples of the most often applied aromatic diisocyanates
final products obtained with their fraction are worse. Generally, aliphatic diiso-
cyanates are less reactive than aromatic.
Isocyanates can be obtained in the reaction of phosgene with aliphatic or aro-
matic amines:
R − NH 2 + COCl 2 = R − N = C = O + 2HCl
amine phosgene isocyanate
However, on account of a high toxicity of phosgene, another method of obtaining
isocyanate, where the initial substrate is nitrobenzene, was developed. Nitrobenzene
Fig. 3.16 Scheme of the synthesis of diisocyanates (without phosgene)
(C6H5NO2) n reaction with ethanol (C2H5OH) and carbon dioxide creates ethyl ure-
thane (NH2COOC2H5). Then urethane is subjected to dimerization in carbonylic
reaction. Finally by heating, urethane decomposes into isocyanate and alcohol
(Fig. 3.16).
Easily volatile isocyanates are highly toxic. Also during a binder hardening the
emission of unreacted isocyanate occurs. The emitted volume depends on a reactiv-
ity of isocyanate. MDI indicates smaller vapor pressure and therefore is less toxic
than TDI. MDI melts at 38 °C, while TDI at app. 20 °C. Diisocyanates can be modi-
fied in order to achieve the needed properties.
In order to accelerate the additive polymerization of multifunctional isocyanates
with hydroxyl compounds, the proper catalysts are applied. They influence a gen-
eral rate of the polymer synthesis as well as a relative rate of individual reactions in
this process. By directing determined reactions, controlling the chain growth rate,
foaming, and hardening rates, it is possible to obtain polyurethanes of optimal,
required properties. Catalysts of isocyanates reactions are divided in two
basic groups:
• Tertiary amines
• Organic metal compounds – mainly bivalent and tetravalent tin compounds.
Amine catalysts are more intensely catalyzing reactions of −NCO groups with
water than with hydroxyl groups. The reactions of −OH group with isocyanates are
accelerated by organic metal compounds much more effectively than by amines.
However, their disadvantage is the fact that they remain in the finished polymer,
while amines, slower or faster, come out of it. An important application of polyure-
thanes is their usage as insulating foams. Foaming occurs when small amount of
water is added during polymerization forming the intermediate product, carbamic
acid, which spontaneously evolves CO2 bubbles. Simultaneous using of both types
of catalysts allows to achieve the necessary balance between the polymer growth
rate and its foaming degree [38, 43–47].
3.4 Furan Resins 101
Fig. 3.17 Raw materials for production of furan resins
3.4 Furan Resins
Furan resins are synthetic resins obtained in polycondensation of furfuryl aldehyde

(furfural) with phenol (furan–phenol resins) or with ketones (especially acetone)
and in polycondensation of furfuryl alcohol (furfurol) with formaldehyde (furan–
formaldehyde resins), with urea and phenol (furan–urea–phenol resins), and with
other substances [8, 48]. These resins undergo cross-linking under an influence of
heating or chemical agents. Some of these resins found applications in casting. The
initial raw material is furfuryl aldehyde, obtained from agricultural leftover, e.g.,
straw, corn cob, and sugar cane (Fig. 3.17).
Furfuryl aldehyde (furfural) is industrially obtained by acidic dehydration of
pentose sugars, contained in wastes of the pulp industry, straw, and bran (oat, rice,
cotton, corn cobs), by means of inorganic acids [49]. As the result of a catalytic
separation of the carbon oxide particle (decarbonylation) from furfural, furan is
obtained (Fig. 3.18). Furfural is a colorless liquid of a characteristic smell of fresh
bread. Furfural is heterocyclic aldehyde, unstable and highly reactive. This is caused
by the presence of carbonyl (C=O)2 group and aromatic ring, which means that
carbonyl group can participate in additional reactions, which can lead to the ring
cracking. On account of this, heating of furan aldehyde in the presence of acids
causes its solidification into thermo-hardened resin. More than 60% of the world
production of furfuryl aldehyde is transformed into furfuryl alcohol, mainly applied
in the production of resins for the casting industry [51].
Furfuryl alcohol is obtained by dehydrogenation of furfuryl aldehyde [50], e.g.,
above a catalyst Cu−Cr (Fig. 3.18).
Furfuryl alcohol can mix with water and several organic solvents such as alco-
hol, ether, and acetone, but not with hydrocarbons. A majority of furfuryl alcohol
(85–90%) is utilized in production of furan resins, applied as binders for molding
and core sands. The world production of furfuryl alcohol is presented in Fig. 3.19.
China is still the largest world producer (80% of the world production) and
2
Decarboxylation – chemical reaction in which carboxylic group, from acids or their salts and
esters, is removed, and due to that CO2 is usually emitted.
Decarbonylation – chemical reaction, in which carbonyl group is removed, which the most
often causes emission of CO.
pentose furfuryl aldehyde

–3 H2O
C5H10O5 CHO
H+ O
Ni 280 °C Cu H2
O
O
CH2OH
furan furfuryl alcohol

Fig. 3.18 Obtaining of furfuryl alcohol and furan from raw plant materials. (Adapted from Ref.
[50])
World consumption of furfural—2015
Middle East
Central/Eastern
Central/South
Europe Other
Africa America
United States
Other Asia
Western Europe
China
Source: IHS © 2016 IHS
Fig. 3.19 World utilization of furfuryl alcohol in 2015. (Reprinted by permission from Ref. [51])
3.4 Furan Resins 103
Fig. 3.20 Self-
condensation reaction of CH2OH + H CH2OH
furfuryl alcohol O O
H CH2 CH2OH
O O
–H2O
CH2OH + CH2OH CH2–O–CH2
O O O O
Fig. 3.21 Reaction of self-condensation of furfuryl alcohol in the acidic environment
consumer (55% of world consumption) of furfuryl alcohol. Moreover the furfuryl

alcohol market grows every year by 6–7%, mainly due to the development of the
automotive industry.
Monomers of furfuryl alcohol can polymerize according to two mechanisms
[14, 52]:
• Chain polymerization or polyaddition, which is initiated by a free radical, cat-
ionic, or anionic activator. As a result of such polymerization macroparticles
with furan side rings in the main chain are obtained.
• The second mechanism contains polycondensation (or condensation polymeriza-
tion). Polymers or copolymers, which are the result of the condensation reaction
catalyzed by acid (pH = 3–5, temperature 80–100 °C), are obtained in a form of
macroparticles with furan rings in the main chain. Furan resins are the most often
obtained by this method.
Polymerization occurs in result of a highly exothermic reaction between −
CH2OH groups and active hydrogen atom (Fig. 3.20).
In result of a condensation of linear oligomers of furfuryl alcohol, furan rings
connected by methylene (−CH2−) and methylene–ether (−CH2−O−CH2−) bridges
are obtained (Fig. 3.21) [38].
Inorganic and organic acids can be used as hardeners of furan resins. The pres-
ence of furan rings provides a possibility of the fast hardening of molding sands by
means of acidic catalysts, at an ambient temperature. These catalysts can be strong
aromatic sulfonic acids, p-toluenesulfonic (PTS), benzenesulfonic (BS), or xylene-
sulfonic (XSA), sometimes with addition of diluted sulfuric or phosphoric acid.
Hardening of furan resins is a highly exothermic process. It can be accelerated by
heat, oxygen, ultrasounds, or additions of phenol and urea [53, 54].
The furan–formaldehyde resin structure hardened by p-toluenesulfonic acid is
shown in Fig. 3.22.
All furan resins contain free furfuryl alcohol, since the largest its content, the
lower resin viscosity. However, on account of the environment protection, there is
S
CH2OH
CH2 OH HO
CH2 CH2 CH CH CH2

CH2
OH HO
CH2 CH2
CH2 CH2 CH2
O O OH
O
CH2 ...
CH2 CH2
O CH2 CH2
O
CH2 O
CH CH2
O O
... OH CH2 H2C CH2 C O
O OH H
CH2 CH2
SO3H
CH2 CH2 CH2 C C CH2 C O

H3C
OH CHO H H
Fig. 3.22 Structure of phenol–formaldehyde modified by furfuryl alcohol and hardened by

p-toluenesulfonic acid. (Adapted from Refs. [55, 56])
a tendency of limiting the content of free furfuryl alcohol and of formaldehyde and
phenol. In the newest resin generations, the free alcohol content is limited to 25%.
The EU Directive classifies furan resins containing less than 25% of free furfuryl
alcohol as harmful, while those containing more than 25% as toxic resins [57].
One of the method of decreasing the free furfuryl alcohol content in resin is its
partial substitution by adding 10% of ethanol [53, 58], which are less harmful than
furfuryl alcohol. Another way of decreasing the free furfuryl alcohol content in
resin is introducing liquid polymerized alcohol. This allows to reduce the content
of furfuryl alcohol monomer to below 25%, whereas the content of free formalde-
hyde can be decreased by adding urea at the last stage of the resin synthesis. The
structure of liquid polymer of furfuryl alcohol and its hardened form is presented
in Fig. 3.23.
Furan resins modified by urea, formaldehyde, and/or phenol, which provide
urea–formaldehyde–furan or phenol–formaldehyde–furan resins, are applied in
molding sands technologies. A modification is based on the introduction into a solu-
tion of given resin, at the early oligomerization stage, furfuryl alcohol, which causes
partial transition of hydroxymethyl (−CH2OH−) groups in ether (−CH2−O−CH2−)
bridges.
The hardening process of furan resin can be also performed by means of ammo-
nium salts of strong acids with urea additions, e.g., aqueous solution of urea and
ammonium chloride or ammonium nitrate with a small addition of modifier. This
3.5 Urea–Formaldehyde Resins 105
Liquide polymer of furfuryl alcohol
HOH2C O O O n O CH2OH
C+
O
OH
O
Cured by strong acids
+additives: Urea-formaldehyde resin
Solvents
Phenol resin
Silanes
O O
HOH2C O O O O O O O O CH2OH
n
O
H2O
HOH2C O O O n O O O O O O CH2OH
n
O O O O O O CH2OH
n Curved furan resin
Curved by strong acids
Fig. 3.23 Transition from furfuryl alcohol to a highly cross-linked furan matrix in furan binder.
(Adapted from Refs. [58–60])
type of hardeners in combination with high temperatures (180–280 °C) is applied in

the casting core hot-box production. Furfuryl alcohol is currently applied as a binder
in the following molds and core technologies: hot-box, warm-box, cold molding
sand hardening (FNB), and molding sand hardening by a gaseous hardener. Studies
concerning thermal decomposition of binders based on furan resin were described
in articles [23, 40, 61–64]. Authors found that the largest amounts of these sub-
stances are formed at a temperature of 900 °C.
3.5 Urea–Formaldehyde Resins
Urea–formaldehyde resins are formed in the two-stage reaction (Fig. 3.24). The first
stage involves the reaction of urea and formaldehyde under neutral or mildly alka-
line conditions, leading to the production of mono- and dimethylol ureas, which are
having hydroxymethyl (−CH2OH) group (Fig. 3.25).
During the second step, these hydroxymethylated urea condense under slightly
acidic conditions to form methylene (−CH2−) and ether bridges between the urea
molecules (Fig. 3.26) [65]. Reaction of obtaining hydroxymethyl derivatives pro-
ceeds in an aqueous environment, due to good solubility of both reagents, and is
catalyzed by hydrogen as well as by hydroxide ions. The pH value decides on the
reaction rate. A form of the final product depends on several factors: catalyst
selection, temperature, pressure, and molar ratio of reagents. As far as subsequent
O O
CH2O
H H H
N N N N OH
H H H H
O O
H –H2O H
n N N OH N N OH
H H H H
n
Fig. 3.24 Two steps in formation of urea–formaldehyde resin
Fig. 3.25 Formation of NH * CH2OH

mono- and dimethylol
ureas in the reaction of HCHO
C O
urea with formaldehyde NH2
(first stage) NH2
C O
NH * CH2OH
NH2 2 HCHO
C O
NH * CH2OH
O O
H2N NH CH2 NH NH CH2 OH
Fig. 3.26 Polycondensation of methyl derivatives of urea with a formation of macroparticles con-
nected by methylene bridges. (Adapted from Ref. [65])
formaldehyde molecules are connecting its reactivity decreases. In practice, a

mixture of mono-, di-, and trihydroxymethylureas [10, 49, 66, 67] is obtained.
This process is the slowest at pH = 4–8. At pH > 8 or pH < 4 the process signifi-
cantly accelerates [68].
Urea–formaldehyde resins dissolve in polar solvents. Hardening (cross-linking)
is initiated by decreasing of pH, and therefore acids are added, e.g., phosphoric or
maleinian. The cross-linking can also occur when a temperature is increased to app.
120 °C and pH < 5 [38, 52, 65]. At first, a linear polymer is obtained (at pH < 4 or
>8) (Fig. 3.27).
References 107
O
O O
C CH2
CH2 C CH2 C CH2 N N OH
OH N N N N
H H
H H H H
n
Fig. 3.27 Formation of a linear polymer
In a presence of a significant excess of formaldehyde, the cross-linked structure

is formed. In the first stage of the reaction of formaldehyde with urea, ammonia is
introduced into the system to reduce the free formaldehyde content in polymer
[18]. Typical urea–formaldehyde resins are currently seldom applied as molding
sands binders. The most often urea–formaldehyde–furfuryl resins, which can be
used in the hot-box technology or Thermoschock, are applied. In such situation
hardeners are phosphoric (V) acid or sulfonic (VI) acids (when resin contains large
amounts of furfuryl alcohol). When the molding sand with urea–formaldehyde
resin is at the preparation stage, formaldehyde is emitted to the atmosphere.
Formaldehyde can be also emitting from the hardened resin, when it will be in the
acidic environment. This is highly disadvantageous on account of a threat for peo-
ple and animals. Therefore studies concerning urea–formaldehyde are mainly con-
centrated on the development of such systems from which would be emitted small
amounts of formaldehyde. During a storage of urea–formaldehyde resin, reactions
causing structural changes can occur. In case of resins – of a small nitrogen con-
tent – for the foundry industry, hexamine as the cross-linking factor is partially
substituted by another cross-linking factor not containing nitrogen. Usually it is
thermo-hardened phenol–formaldehyde resol-type resin. Urea–formaldehyde res-
ins are mainly applied in the wooden materials production, glues, and binders for
molding and core sands.
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Part II
Organic Binder Systems of Molding and
Core Sands
Chapter 4
Aggregate Molding Materials
Materials for sand molds and cores called casting materials can be divided into [1]:
1. Materials constituting matrices of molding sands and protective coatings: quartz
sand, zirconium sand, olivine sand, chromite sand, sintered magnesium, cham-
otte, mullite, corundum, cast steel shot, and others.
2. Agents binding matrix grains:
–– Casting clay
–– Binders
–– Physical factors: negative pressure, electromagnetic field, negative
temperature
3. Auxiliary materials:
–– Molding boxes, materials preventing burning-on the mold material to the
casting surface
–– Materials preventing sticking molding sand to the model instrumentation
–– Special additions improving the determined properties of molding sands
4.1 Silica Sand
Silica sand due to its availability and low price is the most often used as matrix of
molding and core sands. However, in the last time, the situation of silica sands was
changed because the so-called crystalline silica was considered to be the carcino-
genic factor (grains <5 μm, i.e., respirable dust) [2]. The most often the so-called
terrestrial sands are used. Other sands are applied for special castings, when higher
fire resistance, better thermal conductivity, or lower coefficient of thermal expan-
sion are required. Silica sands for casting needs must fulfil several requirements
(Table 4.1).

114 4 Aggregate Molding Materials
Table 4.1 Recommended chemical composition of silica sand applied in castings

Parameter (%) Coarse Medium Fine
Clay 0.15 0.18 0.29
LOIa 0.058 0.072 0.085
pH 7 7.1 7.4
ADVb 0.5 0.8 1.7
Grain shape Rounded Rounded Rounded
SiO2 99.75 99.65 99.51
Al2O3 0.55 0.065 0.12
Fe2O3 0.016 0.018 0.035
TiO2 0.010 0.011 0.016
CaO 0.011 0.012 0.02
MgO 0.008 0.009 0.018
Adapted from Refs. [1]
a
Loss on ignition
b
Acid demand value
Within the range of chemical properties:

• Minimal SiO2 content: 95–96% the more silica, the more fire-resistant sand
• Maximum loss on ignition: 0.5% – determined by the amount of organic
contaminations
• Maximum Fe2O3 content: 0.3%; iron oxide (III) decreases refractoriness
• Maximum CaO content: 0.2% – causes increased need for acids
• Maximum K2O and Na2O content: 0.5% – decreases refractoriness
• Acid demand value (ADV) maximum: 6 ml to pH = 4 – high value of the ADV
is disadvantageous in case of applying binders hardened by catalysts of an acidic
character (e.g., molding sands with furan resin); sands containing basic minerals,
specially sea shells, will be binding acidic catalysts. Sands indicating the ADV
above 10–15 ml are not suitable for molding sand technologies, in which acidic
catalysts are applied.
Grain size distribution of sands influences the casting quality. Sands of large
grains enable the liquid metal penetration inside the mold or core, causing worsen-
ing of casting surfaces. Fine grains provide better surface quality; however, they
require more binders, and the mold has a low permeability, which can lead to cast-
ing defects of gaseous origin.
A majority of silica sands applied for molds and cores have grains within the
dimensional range, 200–250 μm, which assures obtaining good final surface and
low binder consumption (Fig. 4.1).
A majority of silica sands applied in casting houses is characterized by the fol-
lowing properties (Table 4.2):
Silica sands have several faults, when it comes to their application for mold and
core production. They have relatively low refractoriness, which can be the reason of
molding sands burning-on to castings, especially in case of steel castings and heavy
cast iron castings [4]. Silica sands can react with ferrous alloys, especially with
those which contain Mn. Silica reacts with oxides: FeO and MnO forming silicates
4.1 Silica Sand 115
Fig. 4.1 Typical grain size distribution of silica sand. (Adapted from Refs. [1, 3])
Table 4.2 Recommended physicochemical properties of silica sands applied in foundries

Parameter Value Effect
Grain number 50–60 AFS Good final surface of a casting, lower binder
Average grain size 220–250 μm consumption
Dusts content (below 200 Max. 2% Lower binder consumption
mesh = 74 μm)
Clay content below 20 μm Max. 0.5% Lower binder consumption
Specific surface 120– Lower binder consumption
140 cm2/g
Dry permeability 120– Reduction of defects of gaseous origin
150 units
of low melting point which are penetrating deep inside a mold, leading to burnings
on castings.

(
2 FeO + SiO2 = Fe 2SiO 4 ferrous orthosilicate ( fayalite ) , tmelt = 1205 °C )

(
MnO + SiO2 = MnSiO3 manganese metasilicate, tmelt = 1270 °C )

(
2 MnO + SiO2 = Mn 2SiO 4 manganese orthosilicate, tmelt = 1327 °C )
Silica sands are characterized by a high coefficient of expansion, both linear (α)
and volumetric (ß) during heating, as compared with other sands applied as matrix
for molds and cores (Figs. 4.2 and 4.3). This contributes to such casting defects as
buckles, veins, and scars.
Fig. 4.2 Thermal linear expansion characteristic of sands for molds and cores. (Reprinted by
permission from Ref. [5])
Fig. 4.3 Thermal volumetric expansion characteristics of sands for molds and cores. (Reprinted
by permission from Ref. [5])
4.1 Silica Sand 117
The reasons are polymorphous changes to which SiO2 is subjected [6]. During
heating in the air under 1 atm of pressure α-quartz at a temperature of 573 °C
changes into ß-quartz. This change is fast and reversible during cooling. This change
is related to the volume increase by app. 2.5%, which leads to the length change by
app. 1.5% [6]1. At a temperature of app. 873 °C forms ß-tridymite, and at a tempera-
ture of 1470 °C ß-cristobalite is formed [7]. These changes are also related to the
volume increase. The melting point of silica equals 1711 °C [1, 6]. Phase transfor-
mation cause changes in the crystalline structure of quartz which, in turn, leads to
density changes.
α - coefficient of linear expansion

β - coefficient of volumetric expansion
Table 4.3 Grain composition of typical silica sands applied in Germany and Great Britain
Sieve size Great Britain sands Germany sands
Micrometry (μm) Mesh Chelford 50 (%) Chelford 60 (%) H32 (%) H33 (%)
1000 16 trace zero – –
700 22 0.7 0.4 – –
500 30 4.5 2.3 1.0 0.5
355 44 19.8 10.0 15.0 7.5
250 60 44.6 25.7 44.0 30.0
210 72 21.6 23.8 39.0 60.0
150 100 8.2 28.7 – –
100 150 2.6 7.6 – –
75 200 zero 1.3 1.0 2.0
AFS grain fineness 46 59 51 57
Average grain size (mm) 0.275 0.23 0.27 0.23
1
Silica behavior during heating (melting temperature, volume dilatability, or temperature of other
transformations) strongly depends on its origin source, chemical composition, grain sizes, intro-
duced additions, etc. Thus, grain size has a minimal influence on silica sand expansion, but not all
sands have the same increasing degree. Sands containing finer grains are less expanding than sands
containing large grains. The chemical composition has the highest influence on the silica sand
expansion. The expansion of silica sand with binder addition is different than the expansion of sand
alone. This is explained by the fact that several binders during heating undergo decomposition or
burning. In addition, at the beginning of heating binders are undergoing further polymerization.
Therefore, the expansion of molding sand is usually lower than of individual silica grains [26].
Therefore, each phase transition is accompanied by a change in the coefficient of

volumetric expansion (Fig. 4.3).
Sands have a tendency for the segregation, which significantly influences the
grain composition of matrices. This segregation can occur during transportation or
storing in containers. Changes of the matrix grain composition can also occur as a
result of thermal shocks of mechanical influences (mixing, mechanical reclama-
tion). Sand grains can then crack.
Grain analysis of typical silica sands used in foundries in Germany and Great
Britain is shown in Table 4.3.
Grains of German sands are more rounded; less binder is required to obtain by
the sand the required strength. Characteristics of main sands – used in the world –
for matrices of molding and core sands is presented in Table 4.4.
Harmfulness of Respirable Crystalline Silica
Crystalline silica is harmful for health. Quartz being the main version of crystalline
silica is the often applied raw material, among others it is the main raw material in
foundries. Potential, main sources of exposure to silica influences in foundries are
transportation and handling of free and reclaimed sands, forming and producing of
cores, castings knocking out, fettling and finishing of castings, and repairs of ladles
and furnaces. Crystalline silica together with its respirable2 fraction is present in the
abovementioned operations. Employees, who breath these very small particles of
crystalline silica, are subjected to an increased risk of serious sicknesses related to
silica, such as lung silicosis, lung cancer, and other respiratory and kidney diseases.
Crystalline silica in a form of respirable quartz and cristobalite is considered by the
International Agency of Research on Cancer (IARC) as the carcinogeneous factor
for people (group 1.) [8].
4.2 Zircon Sand
Zircon sand due to its physicochemical properties, low thermal expansion, high
specific weight, high temperature resistance, resistance to wetting by liquid alloys,
but simultaneously relatively high price, is applied only for selected alloys and cast-
ings. It can be used for matrices of molding sands as well as core sands. Due to a
low coefficient of thermal expansion castings defects, related to dimensional
changes, can be eliminated. Zircon matrix does not react with SiO2, nor with ferrous
oxides, and due to that such defect as burning-on is eliminated. Zircon sand can be
applied as a matrix of molding sand with chemical binders and of cast steel castings
(contents of free silica limited to maximum 1%). This sand is used in lost foam
technology. Thermal conductivity of the zircon sands is above 30% higher than sil-
ica sands.
On account of a high price of zircon sand, the reclamation of spent sands is nec-
essary. The best, for this aim, is the mechanical two-stage reclamation. Very often
two kinds of matrices are used in the same mold, e.g., facing sand on the zircon sand
Table 4.4 Basic properties of sands use for making of molds and cores
Zirconium/
Aluminum Carbon
Parameter Silica Olivine Chromite Zircon Silicate Staurolite sand
Composition (mas.%) 95% SiO2 SiO2 42% max.; SiO2 2% SiO2 34% max.; Al2O3 49.3%;
4.2 Zircon Sand
MgO 49%; min. max.; ZrO2 65% min. SiO2 29%;

Fe2O3 3% max. MgO 10%; Fe2O3 0.15% max. FeO 17.4%;
TiO2 3.0% max. Fe2O3 26% Al2O3 2.0% max. H2O 4.3%.
Al2O3 3.0% max. max; TiO2 0.35% max.
Cr2O3 44% free silica
min.; 2.00% max.
Al2O3 15%
CaO 0.5%
max.
Color White light Greenish gray Black White brown White brown Dark brown
brown
Hardness 6.0–7.0 6.5–7.0 5.5–7.0 7.0–7.5 6.5–7.0 6.5–7.5
Bulk density 1.36–1.60 1.60–2.00 2.48–2.64 2.56–2.96 2.48–2.69 2.29–2.34 1.03
(g/cm3)
Specific gravity 2.2–2.6 3.2–3.6 4.3–4.5 4.4–4.7 3.2–4.0 3.1–3.8 –
(g/cm3)
Grain shape Angular/ Angular Angular Rounded/angular Rounded Rounded Rounded
rounded
Linear expansion at 1.8 0.83 0.5 0.3 0.5 0.7 –
1600 °C
(% linear changing)
Melting point (°C) 1427–1760 1538–1760 1760–1982 2038–2204 1816–1982 1371–1538 > 2500
Wettability with Easy Generally, not Resistant Resistant Resistant Resistant
molten metal
(continued)
119
120
Zirconium/
Aluminum Carbon
Parameter Silica Olivine Chromite Zircon Silicate Staurolite sand
Size of grains (μm) 83–600 94–375 167–300 94–158 188 2141
Thermal conductivity 1.14a 0.94a 0.63a
(W/mK)
Heat capacity (J/gK) 0.284a 0.235a 0.197a
pH 6.9–7.4 9.2–10.5 5.5–7.0
Comments Forstelite Zircon ZrSiO4 97.0%
Mg2SiO4 93% melting point 2100 °C
melting point. Kyanite (Al2O3 SiO2) 2.0%
1900 °C Rutile TiO2 0.3%
Fayalite Fe2SiO4 ZrO2 melting point 2687 °C
6%
melting point
1205 °C
a
These data refer to the temperature at 1100 °C [11]
4 Aggregate Molding Materials
4.3 Olivine Sand 121
Table 4.5 Chemical Compound Content (%)

composition of zircon sand
ZrO2 + HfO2 63.06–65.50
(mas.%)
TiO2 0.26–0.85
Fe2O3 0.05–0.11
Al2O3 0.13
SiO2 33.1
U and Th Max. 260 ppm
Mineral composition of zircon
sands (standard): zircon (ZrSiO4,
97.0%; kyanite (Al2O3. SiO2),
2.0%; rutile (TiO2), 0.3%; other
minerals, <0.10%
Table 4.6 Chemical Content

composition of typical olivine Compound (%)
sand (mas.%)
MgO 49.7
SiO2 41.3
Fe2O3 7.3
Cr2O3 0.29
Al2O3 0.47
NiO 0.34
MnO 0.09
matrix and backing sand on the silica sand. That time, after the reclamation of the
mixture, both sands are separated by special methods. Good results can be obtained
when a mixture of chromite and zircon sands is applied.
Zircon sands can contain natural radioactive elements such as thorium (Th) and
uranium (U) (Table 4.5), and then the employees using such minerals in their work
have to apply the proper personal protective equipment [1, 4, 12].
4.3 Olivine Sand
Olivine sand constitutes the mixture (90:10) of forsterite Mg2SiO4 and fayalite
Fe2SiO4 (Table 4.6). This sand is sometimes used as the molding sand matrix at
producing castings of high-alloyed steels, mainly high-manganese steel since man-
ganese oxide does not react with silica (which is bound in forsterite and fayalite)
and thus burnings-on do not occur. Olivine sand has lower coefficient of thermal
expansion than silica sand and higher thermal shock resistance, which reduce the
molding sand expansion problem. Olivine sand has a high ADV (it is highly alka-
line) and therefore is not suitable for technologies using acidic catalysts, e.g., mold-
ing sands with furan resins. It can be applied only in technologies based on alkaline
binders (e.g., ALPHASET technology). Since grains of olivine sand are of irregular
shapes, larger amounts of binder are needed for the molding sand preparation.
Advantageous features of olivine sand, such as density, chemical composition,
and thermal properties, which assure obtaining castings of a high dimensional accu-
racy and of a high surface quality, are the reason that this sand is more often applied
as a matrix of molding sands with bentonite, especially in automated lines. The
number of foundries of non-ferrous metals (aluminum alloys, bronzes, and brasses)
using this sand is also growing [13, 14]. Molding sands with alkaline binders (e.g.,
alkaline resol resin hardened by esters) on the olivine sand matrix are difficult for
the reclamation by conventional dry grinding methods, because on surfaces of
matrix grains basic salts are precipitating, worsening binding properties of the
reclaim. Therefore usually three-stage reclamation system is applied: primary rec-
lamation, containing sand disintegration to grain sizes, next the second reclamation
stage during which a binder is removed from surfaces of sand grains (Table 4.7).
When obtaining of a very clean sand is needed, the product after the second recla-
mation stage is subjected to the thermal reclamation (third stage).
4.4 Chromite Sand
Chromite sand is widely applied, especially at making cast steel castings, due to its
relatively low coefficient of thermal expansion and significantly higher (than that of
silica) thermal conductivity coefficient (molding sand on the chromite sand matrix
acts as a chill) (Table 4.8). Therefore, the most often molding sand on the chromite
sand matrix constitutes the facing sand (for medium and large castings), while the
filling sand is molding sand on the silica sand matrix. Such mixing of two kinds of
sands creates certain problems at their reclamation. A segregation of both kinds of
sands occurs by means of the magnetic separation (chromite sand is magnetic, while
silica sand is non-magnetic). However, when this separation is not accurate, too
high fraction of SiO2 in chromite sand worsens its fire resistance (maximum SiO2
Table 4.7 Grain analysis of Fraction

olivine sand (mas.%) Sieve size (mm) (%)
0.355 16.3
0.250 51.2
0.180 24.5
0.125 6.1
0.090 1.4
0.063 0.4
< 0.063 0.1
LOI 0.75
4.5 Other Minerals Used as Matrices 123
Table 4.8 Chemical composition of typical chromite sand (mas.%)

Chemical composition:
Obligatory
Cr2O3 min. 46.0% (average 46.30%)
SiO2 max. 1.0% (average in range 0.60–0.80%)
Recommendation
FeO 26.20% P 0.003%
CaO 0.30% S 0.003%
MgO 9.80% Cr/Fe 1.55: 1
Al2O3 15.50%
ADV:
pH 3 5.60 ml
pH 4 4.50 ml
pH 5 3.30 ml
Grain size: AFS 45 – 50 and AFS 50 - 55
content should be 1%). Chromite sand indicates a high resistance to influences of

metal oxides and slags. It is weakly wetted by liquid casting alloys, due to which a
penetration effect is limited to a minimum [15, 16].
Certain problems occur when chromite sand is the facing sand and molding sand
on the silica sand matrix is the filling sand. In such case, at high temperatures, the
so-called chromite glaze, being the effect of chromite sand sintering with silica,
occurs on the casting surface. In the reaction of iron oxide with silica fayalite, the
component of a low melting temperature is formed. Fayalite is non-magnetic, and it
is not possible to separate it by means of the magnetic separation method. As the
result of sands recycling the amount of substances of low melting temperature
increases, which decreases their fire resistance. An additional problem related to
chromite sand is the fact that at a liquid steel temperature, it is not very durable.
Under oxidation conditions chromite oxidizes to Fe2O3 and Cr2O3, but in the pres-
ence of carbon, originated from organic binders, iron oxide can be reduced to liquid
iron [12]. The examples of requirements of chromite sand for molds and cores are
shown below.
4.5 Other Minerals Used as Matrices
The presented above sands constitute basic aggregate molding materials. Low prices
of silica sand are often the most important argument at choosing matrices for mold-
ing sands, and the influence of this sand on employees’ health and environment is
not satisfying. Therefore the foundry industry is constantly searching for new
materials, which would satisfy requirements not only technological but also in the
ecology and environment protection [17].
Aluminosilicate Sands Representatives of this group of sands are staurolite
(Table 4.9) and kerphalite.
Table 4.9 Chemical composition of silica sand and Fe–Cr slag (%) [19]
Component SiO2 CaO FeO Al2O3 MgO Cr2O3
Silica sand 96.62 0.57 1.02 1.54 0.57 –
Fe-Cr slag 32.20 3.19 2.50 26.39 23.53 12.25
Staurolite
Staurolite (granatyt) – mineral from the silicate group. A common mineral. The
name originates from Greek words stauros and lithos, which mean transverse stone.
Basic aluminum and iron silicate (2(Fe,Mg,Zn)O·AlOOH·4Al2O(SiO4)); typical
mineral of crystalline shales formed by metamorphosis of sedimentary rocks, rich
in aluminum. Due to its high resistance to weathering, it occurs also in sedimentary
clastic rocks.
It can be applied as matrix for molds and cores for castings of Al and Mg alloys,
bronze as well as of gray and spheroidical cast iron. It has a relatively low thermal
expansion, but not high refractoriness (app. 1540 °C). Grains are oval of an average
size: 0.16–0.1 mm.
Kerphalite
This casting sand is based on andalusite, which is produced from a mineral, being
in western France. In order to obtain sands suitable for foundry, casting the produc-
tion regime must be strictly adhered to. Its composition is as follows: Al2O3, 61%;
SiO2, 38%; Fe2O3, 0.5%; and K2O + Na2O + CaO + MgO, <0.5%. Kerphalite can be
applied in all, currently widely applied, molding sand technologies (ALPHASET,
cold-box, Croning, and sands with furan resin). It can substitute zircon sand in case
of cast iron and cast steel castings. This sand does not undergo changes at high
temperatures, due to which problems occurring in molding sands on silica sand
matrix are avoided. Karphalite melting point is above 1800 °C, bulk density 1.7 g/
cm3. This sand has very low coefficient of thermal expansion (app. 0.6% in a tem-
perature range: 0–1000 °C). It mixes well with silica sand [18].
Iron–Chromium (Fe–Cr) Slag
Narasima et al. [19] were tested suitability of Fe-Cr slag as a material for molding
sand matrices, which would be able to substitute, fully or partially, silica sand in the
foundry industry. The assessment was carried out on the basis of molding sands
with water glass hardened by CO2. Fe-Cr slag is a solid waste resulting during
smelting ferrochromium. Its annual production equals 6.5–9.5 million tonnes, and it
is expected that this waste production will be growing by 2.8–3% annually. This
slag has physical and chemical properties similar to silica sand (Table 4.9).
In both materials the main phase is SiO2, but slag contains much less of this
component, while the mixture Al2O3 + MgO constitutes over 50%. There is also
quite large amount of chromium, but it is Cr3+, which is much less harmful than Cr6+.
Both MgO and Al2O3 have much higher fire resistance than SiO2. After a proper
disintegration, grains of similar average sizes are obtained (silica sand 390 μm,
while slag 300 μm). At a comparable average grain size the slag specific surface is
by 50% higher than sand.
4.6 Synthetic Sands 125
Tests of permeability, hardness, shear, and compression strength indicated that

Fe–Cr slag could prove as the matrix of molding sands, substituting completely or
partially sands, out of which molds are made. The most advantageous composition
of sand containing slag as a matrix: 8% of water glass, time of CO2 blowing app.
15 s. Castings made in molds based on Fe-Cr slag, had good final surface without
surface defects and without porosities.
4.6 Synthetic Sands
Synthetic sands of brand names, CERABEADS®, CERATEC®, and CARBO

CERAMICS®, are also applied in casting. They are obtained by sintering or melt-
ing, and due to that, they are resistant to influences of aggressive metals at high
temperatures. These sands contain more than 61% of Al2O3. These are silica–alu-
mina sands based on mullite [20].
CERABEADS®
This is synthetic ceramic sand based on mullite, of spheroidal grains, produced in
Japan. It has a thermal resistance similar to zircon sand and therefore can be applied
for molds of cast steel and large castings of cast iron. It does not undergo burning-on
and is resistant to a liquid metal penetration. Its thermal linear expansion is – in
practice – zero, which allows obtaining castings of a high dimensional accuracy.
CERABEADS® is not radioactive and is produced in several groups of grain sizes.
Its bulk density equals 1.69 g/cm3, pH = 7.2, and melting point 1800 °C [21]. An
exemplary chemical composition is given in Table 4.10, and the grain size distribu-
tion of CERABEADS® synthetic sand is given in Table 4.11.
CERABEADS® is very durable (less weight losses and less dusts produced),
and therefore molding sand on this matrix is suitable for the reclamation, and it is
possible to use up to 97% of reclaim in molding sands with organic binders.
Fused Silica
Fused silica is obtained as a result of ultra-fast cooling of ideally pure, melted or
gaseous silica, obtained artificially. It is a material containing nearly only the amor-
phous phase. It is characterized by nearly zero coefficient of thermal expansion and
by a special resistance to thermal shocks. It is resistant to influences of chemical
substances, except for hydrofluoric acid.
Fused silica is a material of a significantly increased mechanical strength in rela-
tion to normal glass. Due to its elasticity it can be subjected to quite high bending
and tensile loads. It is also relatively resistant to impacts. Fused silica is a glass-like
Table 4.10 Chemical composition of CERABEADS® synthetic sand (%)

Component SiO2 Al2O3 Fe2O3 TiO2 CaO MgO K 2O Na2O P2O5
(mas.%) 36.14 60.57 1.46 0.51 0.14 0.05 0.08 0.27 0.42
Table 4.11 Grain size distribution of CERABEADS® synthetic sand

Grain size (mm) 1.000 0.710 0.500 0.355 0.250 0.180 0.125 0.090 0.063 0.020
Fraction (%) 0.00 0.00 0.02 0.16 21.82 54.40 22.32 1.22 0.06 0.00
material of the highest – out of other known kinds of glass – softening temperature.
It losses its mechanical properties barely above 1100 °C. The basic properties of
melted silica: density, 2.2 g/cm3; compression strength, 1108 MPa; hardness,
600 kG/mm2; maximum utility temperature, 1108 °C; thermal conductivity, 1.38 W/
mK; coefficient of thermal expansion, 0.55 ∙10−6 /K; and specific heat, 740 J/kg∙K.
Carbon Sands
Carbon sands are one of alternatives of foundry sands, assuring obtaining castings
of a high dimensional accuracy, high surface quality, limited burning-on phenom-
ena, and penetrations. In effect, they allow to decrease costs of casting fettling.
Carbon sands are characterized by the following advantages: good permeability,
low thermal expansion, resistance to thermal shocks, small bulk density, and high
thermal conductivity. They are resistant to crushing and have good fluidity and per-
meability. Carbon sands are used in production of molds and cores, but in case of
cores the mixture of carbon and silica sands is applied. Carbon sands can be applied
in a majority of molding sand technologies and can be mixed with other sands.
When the carbon sand fraction equals 50%, protective coatings are not necessary.
These sands are applied for castings of cast iron as well as of non-ferrous metals
[23, 24].
Since carbon sands are produced under controlled conditions, it is possible to
control their grain shapes, grain composition, amount of ignition losses, etc. These
sands can be obtained from calcine petroleum fluid coke [25].
References 127
Appendix 4.1
Fast recalculating matrix grain sizes from AFS system into μm, according to
J. Campbell [12]:
No.AFS x micrometry ( µ m ) = 15 000

AFS 50 = 300 µ m
AFS 75 = 200 µ m
AFS 100 = 1500 µ m
AFS 150 = 100 µ m
AFS 200 = 75 µ m
Approximate change according to AFS grain fitness number into an average
grain size
AFS No. 35 40 45 50 55 60 65 70 80 90
Average grain sands (μm) 390 340 300 280 240 220 210 195 170 150
References
1. Lewandowski JL (1997) Materials for foundry molds. AKAPIT, Cracow (in Polish)
2. (2018) OSHA’s respirable crystalline silica standard for general industry and maritime
3. Goovaerts L, Veys Y, Meulcpas P, Vercaemst P, Dijkmans R (2001) Beste beschikbare techni-
cen voor de gieterijen, Vito
4. Dawson M. Silica sand: foundry requirements and classification. Foundry cast syst & cast-
ing methods Cast Met Serv LDT, https://www.academia.edu/19130829/SILICA_SAND_
FOUNDRY_REQUIREMENS_AND_CLASSIFICATION, Access 09.11.9019
5. Brown J (2000) Foseco ferrous foundryman’s handbook, 11th edn. Elsevier/Foseco
International, Woburn
6. Ringdalen E (2005) Changes in quartz during heating and the possible effect on Si production.
JOM 67:484–492
7. Holmquist SB (1960) Conversion of quartz to tridymite. J Am Ceram Soc 44:82–86
8. Maciejewska A, Krol M (2014) Respirable crystalline silica : quartz and cristobalite. Princ
Methods Assess Work Environ 3:103–119. (in Polish)
9. Webster PD (1980) Fundamentals of foundry technology. Portcullis Press, Redhill, UK
10. Hughes D (2016) Reclaimed sand in foundries. Matarials Foseco Aust
11. Mod Cast 2007;March:26
12. Campbell J (2011) Complete casting handbook, 1st edn. Elsevier Ltd, UK
13. LaFay VS, Neltner SL, Ziegler M (2010) Bonding properties in sand. AFS Trans:118:115–130
14. LaFay VS, Neltner SL, Ziegler M, Thiel J (2012) Replacement of olivine with silica sand in
non-ferrous foundries. AFS Trans: 120:1–16
15. Scott WD, Thomas EM, Strohmayer LL (2003) Quality issues in the selection of chromite
sand for steel foundry use. AFS Trans 111:517–527
16. Drużewski MA, Muravo YN (2013) Burning-on on large sand steel casting faced with chro-
mite. LitProizy 8:11–14
17. Tihon G, Sicot S (2010) Search for substitute sands to replace chromite and zircon. Fonderie
Mag 4:19–33
18. Frulli D (2013) Use of Kerphalite KF as a foundry sand in steel and iron casting. Proceed. Mat.
Int. Conf. Foundry Mold. Mater. Sand Team. pp 175–179
19. Narasimha MI, Babu RJ (2017) Ferro chrome slag: alternative mold material in ferrous and
non-ferrous foundries. Int J Met 11:598–628
20. Schafer JM, Kramer J, Schafer J (2009) Der neue formgrundstoff CERATEC als alternative zu
zirkon – und chromitsand. Giesserei-Praxis 12:404–406
21. Wakita K, Matsubara M (2015) Characteristics and application of the round ceramic base sand
CERABEADS. Slevarenstvi 7–8:24–28
22. ITOCHU CERATECH Corporation (2017) http://www.itc-cera.co.jp/english. Access 20 Dec
2017
23. Gentry EG, Lear C (1961) Calcined fluid coke as new molding medium-preliminary evalua-
tion. AFS Trans 69:320–327
24. Gentry EG (1966) Thermal stability of carbon sand and other non-silica molding materials.
AFS Trans 74:142–149
25. Budihardjo MA, Chegenizadeh A, Nikraz H (2015) Investigation of the strength of carbon-
sand mixture. 7th World Congr. Part. Technol. pp 634–639
26. Thiel J, Ziegler M, Dziekonski P, Joyce S (2007) Investigation into the technical limitations of
silica sand due to thermal expansion. AFS Trans 115:383–400
Chapter 5
Division of the Molding and Core Sands:
Criteria
Molds for metalcasting may be classified in two large groups:

• Lost mold (single used molds): these are specially made for each casting and are
destroyed after pouring. The molds are generally made of sand.
• Permanent molds (multiuse molds): these are used for gravity and low-pressure
casting, pressure die casting, and centrifugal casting.
The cores used for ferrous castings are practically always made of sand. Generally
cores are produced by the same techniques as molds. Small- and medium-size cores
are often blown or shot into core-box.
Regardless of the fast development of permanent mold casting processes, espe-
cially concerning non-ferrous metals alloys, the most popular material for molds
and cores is still sand. Sand has several advantages; however it is not a perfect mate-
rial. It specially concerns technologies of chemically bound sands. The problems
can be caused by such sand properties as grain shape, chemical composition, pH,
fire resistance, clay content, grain composition, and contaminations content. When
a mold or core is in contact with liquid metal, as the results of a heat influence
thermo-mechanical and thermo-chemical processes occur, causing dimensional
changes at the mold/casting boundary, which negatively influence the casting
quality.
According to J. Campbell “Excellent binder should have small viscosity, such
which causes that produced sands are of a good fluidity and after setting are strong
and as small as possible amounts of binders can be used. These sand should not be
reacting with metal, regardless of its temperature” [1]. Future sands applied for
molds and cores will have to meet requirements of modern foundry plants, it means
they have to produce castings which will satisfy or even exceed the clients’ needs.
The future client will require a higher dimensional accuracy of castings, lower price,
and “just in time” delivery, to minimize storing. Simultaneously the foundry manag-
ers strive to improve the quality of produced castings, to increase the production, to
improve work conditions, to meet the requirements of future regulations concerning
the environment protection, and – in consequence – to reduce the casting production

130 5 Division of the Molding and Core Sands: Criteria
costs. More and more complex shapes of castings require maintaining high
dimensional stability, to be able to compete with permanent mold castings, per-
formed in metal molds. Therefore modern foundries more and more often apply
molding and core sands chemically bound, since they have such advantages as easi-
ness of forming and good final casting surfaces. The kind of bonding material
decides on a dimensional stability. Chemically bound sands ensure obtaining these
parameters better than green sands [2]. These specially concerns production of cast-
ings of complex shapes, thin-walled, of good surface, and high yield. However, in
the world, still more than 70% of cast iron castings is produced in green sands [2]
(Fig. 5.1).
In dependence of the assumed criterion, a few divisions of molding and core
sands can be done. The basic division can be done, e.g., on the bases of their desti-
nation: sands for molds and sands for cores. Moreover, the majority of technologies
is used for producing both, molds and cores.
Out of basic kinds of technologies, green sands are – in practice – applied only
for mold production, while some chemically bound sands are used for producing
molds and cores and some for core production only (e.g., hot-box technology).
Cores require sands of different physical properties than molds, and due to that the
binding material applied for core production must be different or introduced in
higher amounts than the one applied for mold production. The selection of tech-
nologies depends on dimensions and amounts of cores or molds, the required pro-
duction rate, available equipment, etc. A very important feature of sands applied for
making cores is easiness of controlling their properties. Such features have molding
sands chemically bound [3]. The fractions of individual technologies of making
molds and cores, in the European Union (EU) countries and in the USA are shown
in Table 5.1.
Fig. 5.1 Fractions of green sand molding in technologies applied for cast iron production.
(Reprinted by permission from Ref. [2])
5 Division of the Molding and Core Sands: Criteria 131
Table 5.1 Fractions of individual technologies of making molding and core sands in the foundry
industry of EU and the USA
EU US
Technology (%) (%)
Furan, acid catalyzed (FNB – furan no-bake) 44 19
Polyurethane (phenolic isocyanate), hardening by liquid amine (PUNB – 3 25
phenolic–urethane no-bake)
Hot-box 2 2
Molds with inorganic binders 2 2
Resol–ester (ALPHASET) 14 8
Mold with phenolic–urethane, gas hardening 32 37
(PUCB phenolic–urethane cold-box)
Shell mold 3 5
Others 1 2
The binder kind and its setting mechanism can influence defects and microstruc-
tures of castings as well as emissions in the workplaces.
As can be seen in Table 5.1, the molding sand with phenolic–urethane no-bake
(PUNB) (liquid amine) is the dominating (25%) technology in the USA. This tech-
nology is – in practice – not used in EU countries.
In EU countries as many as 44% of castings are made of molding sands with
furan resin acid catalyzed, while in the USA, this equals 19%. Growing interests,
both in Europe and in the USA, arouse production technologies of sands with phe-
nol–formaldehyde resol resin, hardened by esters (ALPHASET). Within the core
sands the most popular is the cold-box polyurethane technology (PUCB).
Molding sands with organic binders indicate several advantages in comparison to
green sand, namely, they provide better dimensional accuracy of castings, are more
suitable for castings of complex shapes, have better final surfaces, and provide a
possibility of controlling the time, after which the pattern can be removed from the
mold [6–8].
Systems of Dividing Molding Sands, Based on Sand Matrix, Applied for
Molds and Cores
Molding sands can differ from each other according to their composition, binding
methods and consistency. They have various applications not only concerning the
casting materials, cast iron, cast steel, and non-ferrous metals, but also concerning
their function during forming (facing sand, backing sand). On account of this, it is
difficult to develop the explicit division containing all sands applied in the foundry
practice. Therefore a few systems taking into account dividing of sands in depen-
dence of the assumed criterion were developed.
According to [3], molding sands can be divided in dependence of their:
• Destination:
–– For iron castings
–– For steel castings

–– For non-ferrous metals castings
• Application at forming:
–– Facing sand
–– Backing sand
• The function, which they have in a mold:
–– Unit sand
–– Core sand
• Wear degree
–– Initial – molding sand prepared from fresh components
–– Used – or return molding sand
–– Rebound sand – used sand supplemented by addition of fresh materials
–– Spent sand – the part of used sand which is not subjected to the rebounding
process, but is either directed to the reclamation or to the dump
Assuming the chemical character of the binding material as the criterion – this
division can be as follows:
• Inorganic binders (cement, water glass, phosphates, clays, bentonite,
geopolymers)
• Organic binders (natural and synthetic resins, oils, starch, molasses, biodegrad-
able substances)
• Special sands (lost foam process, investment casting method, frozen sands, vac-
uum process V)
The temperature at which the hardening process occurs can be also the dividing
criterion:
• Setting at room temperature (e.g., molding sands with furan resins, with phenol–
formaldehyde resins, with water glass hardened by liquid hardener)
• Hardened at an increased temperature (e.g., sands in the warm-box technology)
• Hardened at high temperatures (e.g., sands in the hot-box technology)
Division based on a composition, binding way, and consistence, according to [3].
Molding sands with binding material:
• Classic molding sands (synthetic sands, natural sands, clay sands)
• Self-setting molding sands with inorganic binders (sands with cement, with
water glass, gypsum sands, sands with ethyl silicate, sands with colloidal silica)
• Self-setting molding sands with organic binders (e.g., with furan resin, with phe-
nol–formaldehyde resin, with phenol resin hardened by esters)
• Loose, fast-setting molding sands (e.g., sands with water glass, with inorganic
binders, with organic binders)
• Loose slow-setting molding sands
• Loose fast-setting molding sands (e.g., Croning process, hot-box process, warm-
box process)
• Molding sands without binding materials (frozen molds, full mold process) [3]
Assuming as the molding sand division criterion, the way of their setting (accord-
ing to [9]), it is obtained:
• Cold setting at an ambient temperature
Setting of these molding sands occurs at an ambient temperature. The setting
process starts when the last component is introduced into a mixer:
–– Furan resin + sulfonic acid
–– Phenol resin + sulfonic acid
–– Polyurethane + pyridine derivative (PEPSET process)
–– Resol resin + ester (ALPHASET process)
–– Alkyd resin + isocyanate
–– Water glass + ester
• Setting by gases (amines, CO2, SO2)
• Thermosetting – hot curing processes, thermoshock
In the above technologies, setting occurs due to heating a mixture of molding
sand and resin or – more often – by contact of this mixture with the hot pattern.
–– Warm-box
–– Hot-box, phenolic, and/or furan based
–– Molding sands with water glass hardened by a temperature (processes:
AWB®, CORDIS®, INOTEC®)
• Molding sands with bentonite (green sands)
• Molding sands without a binder
–– V-process
–– Frozen molds process
–– Lost foam
• Lost foam technology
• Full mold
Assuming as the criterion the technical level, several molding sands can be
identified [10]:
• I generation molding sand – with clay (bentonite)
• II generation molding sands – with organic and inorganic binders
• III generation molding sands – without binding materials or bound by physical
process: lost foam, full mold, V-process, frozen molds
• IV generation molding sands – with binders of biological origin
The division of molding and core sands, in the hereby paper, was performed
according to their hardening method (this is in conformity with the division
assumed in [9]). The authors limited the described technologies to the ones which
are presently applied in the industry, or are having perspectives for their wider
implementation, or constituted – in the past – the base of producing castings in
sand molds, or which just seemed interesting for the authors. Special sands were
described separately (e.g., lost foam).
Admittedly, traditionally, molding and core sands are distinguished, but – accord-
ing to [3] – more and more often only one expression is used, either molding sands
or core sands. One name “casting sands” will be used in this work, when it is not
necessary to divide sands into molding and core sands.
The selection of the technology for producing molds and cores depends on
dimensions and amounts of cores or molds, required yield, available equipment,
conditions of work, etc. Currently, the most widely are used processes belonging to
the green sands (molds) or sands with chemically bound binders (cores).
Sands with bentonite (green sands) are and will remain the most important and
most widely applied technologies. These sands are cheap and environment-friendly
(provided that additions of substances containing carbon are not used, since they
generate toxic and smelling gases at high temperatures), and – what is the most
important – they are reversible. This technology is efficient: applying chemically
bound sands, it is possible to produce 60–100 molds/hour. Modern casting house,
which uses green sands, can produce 600 molds/hour. The most often used additions
generating lustrous carbon are dust of hard coal, brown coal, pitch, and asphalt.
A certain defect of these sands constitutes their low plasticity, and due to that,
when sands grains are not very strongly bound, the mold after hardening can be
damaged producing shortages. Hardness limits for green sands are determined as
1.0 MPa [1]. These sands have also a relatively low strength in a green state, and this
limits dimensions of castings which can be made in wet molds [3].
Their “greenness” is related to their weakness, plastic condition, contrary to
dried molds having extreme hardness and stiffness. Green sands are often consid-
ered as sands with inorganic binder (it is so assumed in the hereby handbook) [11].
Among chemically bound binders two groups can be distinguished: organic and
inorganic binders. More and more complex shapes of castings require maintaining,
among others, high dimensional stability to be able to compete with permanent
mold castings, performed in metal molds. Therefore, modern casting houses more
and more often apply molding and core sands chemically bound due to their advan-
tages, such as easiness of forming, good final surface of casting, compliance, better
dimensional accuracy, and a possibility of controlling the work time1 and strip time.2
Molding sands with chemical binders assure obtaining these parameters in a higher
degree than green sands. This specially concerns castings of complex shapes, thin-
walled, of a good surface, and highly efficient [6–8].
1
Work time is the property determining time – calculated from the moment of coming into contact
of all components necessary for sand binding. During this time, a sand is suitable for forming
(making molds or cores).
2
Strip time – the period after which a core can be removed from a core-box or a pattern from a
mold without causing damages.
In case of sands with chemically bound binders, a binder and hardener start
reacting immediately after mixing, which causes that these sands have a limited
work time1 and short strip time2 (Fig. 5.2). When a sand work time is exceeded, the
final strength of the sand will be reduced. Usually the sand work time equals 1/3 of
its strip time and can be controlled by the hardener type and by the rate of its adding.
These both times are selected in dependence of the kind and dimensions of molds
or cores which are to be made and in dependence of the mixer capacity. In case of
some binders their initial reaction rate is slow and then increases, which causes that
the ratio of the work time to strip time is large. This is advantageous in case of fast-
setting technologies, since it provides longer times for making a mold or core [12].
The typical pathway of the hardening curve of self-setting sands is presented in
Fig. 5.2.
Various kinds of resins applied for production of molds and cores, together with
their utilization for casting alloys, are shown in Table 5.2 [13, 14].
In case of producing cores, technologies using sands with chemically bound
binders are dominating. Cores require different physical properties than molds.
Cores have to withstand large forces, which can occur in a moment of filling the
casting mold with liquid metal and often have to be removed from small spaces in
the solidified casting. This means that binding material must be such that ready
cores will have high strength properties and after being poured with liquid metal
will disintegrate to be easily removed from the ready casting. On account of this,
cores are usually made of high-silica sand (sometimes of olivine, zirconium, or
chromite sands) and strong binding materials. The most often, these are the same
sands, as the ones used for making molds, but with a larger binder fraction and
100% of fresh sand.
Technologies applied in EU for producing molds and cores are listed in Fig. 5.3a
while technologies of producing cores of sands with chemically bound binders in
Fig. 5.3b.
Fig. 5.2 Typical pathway kPa

of hardening curve of 3500
self-setting sands (Tw. work
time; Ts, strip time; Tc, 80% max
casting time; Tmax, time to
achieve the maximum
Compression
strength). (Adapted from

strength
Ref. [12])
350
10
TW TS Tc Tmax
Time
136
Table 5.2 Resins applied for production of molds and cores as well as the possibility of their using for the given casting alloy
Hardening Mold Core Curing Hardening
type Resin type production production temperature time (a) Metal type Size of series
Cold -setting Furan Medium to Some 10–30 °C 10–120 min Ferrous + non-ferrous Small to large
large
Phenolic Large No 10–30 °C 10–180 min Ferrous Small to large
Polyurethane (Pepset/ Small to Some 10–30 °C 5–60 min Ferrous + non-ferrous Small to large
Pentex) medium
Resol ester (ALPHASET) Small to large Some 10–30 °C 5–400 min Ferrous + non-ferrous Small to large
Alkyd oil Large Some 10–30 °C 50 min Steel Small
Silicate water glass Medium to No 10–30 °C 1–60 min Ferrous + non-ferrous Small to large
large
Gas hardening Phenolic/furanb (Hardbox) Small Yes 10–30 °C <60 s Ferrous + non-ferrous All
Polyurethane cold-box) Small Yes 10–30 °C <60 s Ferrous + non-ferrous All
Resol (BETASET) Small Yes 10–30 °C <60 s Ferrous + non-ferrous All
Acryl/epoxy (Isoset) No Yes 10–30 °C <60 s Ferrous + non-ferrous All
Silicate Small Yes 10–30 °C <60 s Ferrous + non-ferrous All
Thermosetting Oil Small Yes 180–240 °C 10–60 min Ferrous Small
Warm-box Seldom Yes 150–220 °C 20–60 s Ferrous Medium to large
Hot-box Seldom Yes 220–250 °C 20–60 s Ferrous + non-ferrous Medium to large
Croning Yes Yes 250–270 °C 120–180 s Ferrous + non-ferrous Large
Adapted from Refs. [9, 13, 14]
a
That is, the release time – the time with the mold/core has gained sufficient strength to be released from the pattern
b
Not applied for capacities <20 tonnes/day
5 Division of the Molding and Core Sands: Criteria
Fig. 5.3 Technologies applied in EU for producing molds and cores (a) and technologies of pro-
ducing cores with chemically bonded sands (b). (Adapted from Refs. [1, 15])
Consumptions of various resins, catalysts, hardeners, and additions at prepar-

ing chemically bond sands are shown in Table 5.3 [13, 16].
Due to the hazard for the environment and employees, caused by sands with
organic binders, intensive research is carried out to apply natural polymers as
binders, i.e., biopolymers (peptides, starch, collagen) and synthetic polymers
138
Table 5.3 Consumption of various resins, catalysts, hardeners, and additions at preparing chemically bond sands
Hardening Resin addition on Catalyst/hardener addition Additive Additive addition on
type Resin type sand weight, (%) Catalyst/hardener type on resin weight, (%) type sand weight, (%)
Cold-setting Furan 0.8–1.5 Sulfonic acid 25–60 Silan 0.1–0.2
Phenolic 1–2 Sulfonic acid 25–50 n.a. n.a.
Polyurethane 0.8–1.5 Pyridyne derivative 2–6 n.a. n.a.
Resol 1.0–1.5 Ester 25–40 n.a. n.a.
Alkyd oil 1.0–2.0 Isocyanate 18–20 Catalyst 0.002–0.2
Ester silicate 2.0–4.5 Ester 10–15 n.a. n.a.
Gas hardening Phenolic/furan 0.8–1.2 SO2 0.3–3 Peroxide 0.1–0.5
Polyurethane cold-box 1.0–1.8 Amine 0.10–0.15 n.a. n.a.
Resol 1.2–1.8 Methyl formate 0.3–0.5 n.a. n.a.
Resol 2–2.5 CO2 0.7–1.25 n.a. n.a.
Acryl/epoxy 1.2–1.6 SO2 0.02–0.05 Peroxide 0.05–0.06
Silicate 2–4 CO2 1–2 n.a. n.a.
Thermosetting Oil 0.8–4 n.a. n.a.
Warm-box furfuryl 1.0–1.5 Cu salts of sulfonic acids 10–30 n.a. n.a.
alcohol based
Hot-box phenolic or 1.2–3.0 Ammonium salts 10–25 n.a. n.a.
furan based
Croning phenolic 1.5–5 Hexamethylenetetramine 15 n.a. n.a.
n.a. not applicable
5 Division of the Molding and Core Sands: Criteria
(polylactide, polycaprolactam), which are biodegradable. The most often polymers

are applied as additions to the already existing binder, organic or inorganic, in order
either to improve some parameters or to generate new features, which sands without
these additions do not have [17–23]. Efforts of developing the binder, in which a
polymer (e.g., α-starch) will be the basic component, are also undertaken. One of
the first this type binders was the protein composition, containing polypeptides of
natural origin, called GMBOND™, developed by the Hormel Foods Company
(1996) [23]. This binder is well dissolving in water, and the binding process occurs
due to dehydration. This process is reversible, which means that water addition to
hardened binder causes that it regains its binding ability. It has only a small negative
influence on the environment and is not hazardous for people. The obtained castings
meet the basic requirements concerning the dimensional accuracy, do not have ther-
moplastic deformations, and are achieving very good surface quality. Spent sands
from the GMBOND™ technology are easily biodegraded. Investigations indicated
that the application of this binder reduced more than 90% of the VOC emission as
compared with the emission from sands bond by phenol–urethane resins. Due to the
easiness of the degradation of sands with GMBOND™ binder they can be applied
for production of non-ferrous metal castings.
The chronological order of an introduction into the industry individual technolo-
gies of molding and core sands is presented in Table 5.4.
Two groups of factors are taken into account at selecting the technology of pro-
ducing molding sands for molds and cores:
• A group related to dimensions and quality of produced castings: yield, necessary
machines and equipment, sand compactability, work time, fluidity, reclaiming
ability, and costs
• A group related to the natural and work environment: emissions during making
molds and cores as well as emissions and the air contamination during molds
pouring, cooling, and castings knocking out, a necessity of applying protective
coatings, erosion resistance, and elution of harmful substances from spent sands
Assessment Methods of Sand Harmfulness
Two aspects should be considered at the assessment of the given sand harmfulness.
• Molding sand harmfulness for employees and for the environment caused by
emissions of gaseous and dust contaminations occurring during the sand prepa-
ration, producing cores and molds as well as at molds pouring with molten
metal, cooling, and castings knocking out (Fig. 5.4) [26].
These are the following operations:
1. Evaporation of volatile compounds during producing molds and cores (mixing,
sand shooting, molds making, storing, etc.).
2. Evaporation of unreacted initial components of resins (e.g., in case of phenol–
formaldehyde resin: monomers of phenol and formaldehyde) as well as solvents
of higher boiling points at the first seconds after a mold filling with liquid metal.
Table 5.4 History of mold and core making processes

Year Process Resin/binder
Bronze Loam sand Clay
Age
Bronze Investment casting Clay
Age
1944 Croning process, shell mold Phenolic–novolac resin
1951 Shaw process Ethyl silicate
1958 Furan no-bake Furan resins, urea resins
1958 Phenolic acid catalyzed no-bake Phenolic resin
1962 Hot-box Urea, furan and phenolic resins
1965 Phenolic no-bake Phenol resols
1966 Nishiyama process Water glass with silicon
1967 Phenolic CO2 cold box Phenol resin
1968 PUR-cold-box, gas curing process Ortho-condensed resols
1968 Phenolic/urethane/amine cold-box process Phenolic resin
1968 Water glass–ester process Water glass
1970 Phenolic–urethane no-bake (PUNB) Phenolic resol
1971 Furan SO2, gas curing process Furan condensed resin
1978 Warm-box Modified furan resins
1981 Warm-box-vacuum Furan or phenol resols
1982 Ester curing no-bake (ALPHASET) Phenolic formaldehyde resol resin
1983 Cold-box plus, gas curing process Ortho-condensed resols
1983 Cold-box process, curing by methyl formate Phenolic formaldehyde resol resin
(BETASET) (alkalic)
1984 Epoxy-SO2, gas curing process Modified epoxy resins
1987 Hot-box plus Modified phenol resols
1988 Acetal (methylal), gas curing process Resorcinol resins
1995 The beginning of inorganic modified binders Curing of water glass by drying
3. Emission of BTEX and other decomposition products occurred as the pyrolysis

result of the main carbon chain of the polymer in further stages of the casting
production.
The harmfulness of gases emitted during the mentioned operations depends on
their composition and concentration. For several substances their highest allowable
levels at work places were determined. The lower are values of these coefficients,
the more dangerous is the substance.
The coefficients of emission of substances from the HAP group during thermal
decomposition of selected organic binders (stages of pouring, cooling, and knock-
ing out are taken into account) are shown in Table 5.5.
The comparison of gas evolution rates of various sands, with bentonite, with
furan resin and resol alkali resin, as well as with inorganic resins based on sodium
silicate and geopolymer, is shown in Fig. 5.5. As it results from the performed
investigations, the gas evolution rate depends of the binder kind and its content in
Fig. 5.4 Air emission sources during preparing of sands and producing castings. (Reprinted by
Table 5.5 Emission coefficients during thermal decomposition of selected organic binders
HAPa kg per 1 Mg of molten HAPa kg per 1 kg of
Process metal binder
Polyurethane no-bake (1.1% binder) 0.690 0.012
Furan no-bake (1.2% binder) 0.358 0.006
Resol ester no-bake 0.364 –
Polyurethane cold-box (1.75% 0.180 0.019
binder)
Phenolic-ester cold-box 0.553 0.006
a
HAP – hazardous air pollutant
the sand [28]. Out of the tested sands the highest gas evolution rates characterized
sands with resin-based binders. Sands with inorganic binders indicate lower gas
evolution rates than green sands and organic binders.
The measurements results of selected toxic substances released from various
molding sands technologies under a high temperature influence (iron castings) are
presented in Table 5.6 [30]. It can be seen that within the range of tested substances
(total dust, polycyclic aromatic hydrocarbons, and benzo(a)pyrene), the green sands
and with additives generating lustrous carbon are the most dangerous.
• The sand harmfulness for the environment is caused by elution of dangerous
substances from spent sands. In dependence of the concentration of eluted sub-
stances – determined in the elution test – the given sand can be classified to
dumping grounds. In the situation when the spent sand will be further
economically utilized, performing the elution test is also necessary due to a pos-
sible contact with employees or with the environment.
Fig. 5.5 Comparison of gas evolution rates of sands with organic and inorganic binders and for
green sands: Sinotherm®, alkaline phenolic resole resin; Kalltharz X 850®, furan resin; Geopol®
and Rudal®, inorganic binders. (Reprinted by permission from Ref. [29])
Table 5.6 Emission of dangerous substances from molding sands (total dust, PAHs, B(a)P)
Process Mold: metal Total dust (mg) PAH (mg) B(a)P* (mg)
Green sand 3.3 1.625 1.021 1.20
Water glass + ester 2.8 0.017 0.013 0.010
Polyurethane 2.4 0.23 0.007 0.007
Furan resin 3.4 0.050 0.010 0.012
Shell mold 0.90 0.157 0.107 0.021
B(a)P* – benzo(a)pyrene
All chemically bound binders can create potential hazard for the health in case of
long-lasting or recurring exposures to hazardous factors. The threat can occur both
by inhalation and through the skin. Especially dangerous is a direct contact of an
employee with unreacted resin or unhardened sand, during its preparation and dur-
ing making molds and cores. In extreme cases the skin contact with those sub-
stances can cause chemical burns, scars, and allergies. Therefore using personal
protection devices, such as gloves resistant to chemicals, safety goggles, and protec-
tive clothing, is necessary.
During molds pouring with molten metal the binder thermal decomposition
occurs. A majority of decomposition products occurs in trace amounts. Special dan-
gerous are decomposition products of substances containing carbon applied as addi-
tions for green sands. There seems to be a perception that the CO concentration can
be a good indicator of the conditions quality during pouring, cooling, and casting
knocking out [31, 32]. When this concentration is below 50 ppm, the other sub-
stances will be emitted in trace amounts.
References

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environmental and energy concerns in sand foundries. AFS Trans 115:997–989
4. Huttenes-Albertus company, GmbH and HA Internatinal (2014) www.ha-international.com.
Accessed 15 Dec 2016
5. Trinowski DM (2016) Comparing molding and core making trends in the U.S. and EU casting
industries. Hüttenes-Albertus Chem. Werke GmbH
6. Giese SR, Roorda SC, Patersson MA (2009) Thermal analysis of phenolic urethane binder and
correlated properties. AFS Trans 102:355–366
7. Thiel J (2011) Thermal expansion of chemically bonded silica sand. AFS Trans 116:369–378
8. Khandelwal H, Ravi B (2015) Effect of binder composition on the shrinkage of chemically
bonded sand cores. J Mater Manuf Process 30:1465–1470
9. European Commission (2005) Integrated pollution prevention and control reference document
on best available techniques in the Smitheries and Foundries Industry
pojiv, Brno
11. Polzin H (2014) Inorganic binders for mould and core production in the foundry. Schiele and
Schon Gmbh, Berlin
Woburn
13. European Commission (2015) Best Available Techniques (BAT) reference document for the
propuction of pulp, paper and board. Industrial Emission Directive 2010/75/EU (Intergated
Pollution Prevention and Control). https://doi.org/10.2791/370629
cen voor de gieterijen. Vito
16. TWG (2003) Comments to the second draft on Integrated pollution prevention and control
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characterization and comptatioal study of poly (ɛ-caprolactone) based nanocomposites. Mater
Sci Technol 20:15–18
18. Zhou X, Yang J, Qu G (2004) Adhesive bonding and self-curing characteristics of α- starch
based composite binder for green sand mold/core. J Mater Sci Technol 20:617–621
19. Yu W, He H, Cheng H, Gan B, Li X (2009) Preparation and experiments for a novel kind of
foundry core binder made from modified potato starch. Mater Des 30:310–313
20. Makino H, Kato Y, Zenpo T, Asano N (2005) Molding simulation and experiment of new core-
making system with polysaccharide-based binder. AFS Trans:333–340
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polysaccharide. AFS Trans 113:327–332
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23. Parker D, Herreid R (2005) Staying competitive and environmentally compliant. Foundry
Manag Technol 133:27–28
24. Lessiter MJ, Kotzin EL (2002) Timeline of casting technology. Eng Cast Solutions 4:76–80
tions, safety and ecology. Springer Verlag, Berlin, Heidelberg
26. Archibald J, Kroker J (2013) High efficiency cold box processes – technology focused on busi-
ness goals. Int J Met 7(2):51–59
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Forum Mold Mater Cast Technol:110–117
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85:203–308
Chapter 6
Cold-Setting Processes (No-Bake)
Hardening of these molding sands occurs at an ambient temperature. The hardening

process starts at the moment when the last component is introduced into the mixer.
When cores and molds are produced without the need of drying or heating, the
process is called no-bake process. Dry sand is preliminarily mixed with liquid or
pulverized catalyst and then with a binder. The molding sand produced in such a
way should be used as fast as possible, since as time goes by this sand will have
lower and lower tensile strength and compactibility, which – in consequence – can
be the reason of various casting defects, such as metal or buckle penetration. A rela-
tion between a life time and strip time in molding sands of no-bake type depends on
a catalyst, temperature, water content, and wetness of surroundings. A hardening
time can vary from a few minutes to a dozen or so hours. Processes of the no-bake
type contribute to limiting the environment pollution and are reducing the energy
consumption.
6.1 Furan Acid Catalyzed
Furan resins in the no-bake self-setting sands technology were introduced into a
foundry practice in 1958, as furan–urea resins, while 2 years later these resins were
applied in the hot-box and cold-box technologies.
They are used in producing molds and cores for medium and large castings of
nearly all alloys. Certain limitations occur in case of steel castings when resins of
small nitrogen content should be used (possibility of occurring cracks or pinholes)
as well as in case of spheroidal or vermicular cast iron (sulfur presence can degrade
graphite). Furan binders are based on furfuryl alcohol, which is obtained from veg-
etable wastes, such as corn or rice scales. Arylsulfonic acids or phosphoric acid are
usually hardeners. Furan resins are comparable to phenol resins, in their hardening
mechanism and applied catalysts. Adding of an acidic catalyst to furan resin causes
its exothermal polycondensation and binder hardening. In order to increase the

146 6 Cold-Setting Processes (No-Bake)
r eactivity of furan resins, they can be modified by additions of another resin. Thus,
the systems shown below are obtained. The following resin systems are possible:
• Furan resin FA
• Urea–formaldehyde resin–furfuryl alcohol UF-FA
• Phenol–formaldehyde resin–furfuryl alcohol PF-FA
• Urea–formaldehyde–phenol resin–furfuryl alcohol UF-PF-FA
• Resorcinol–furfuryl alcohol R-FA
Silane is nearly always added to a binder, to increase the binding force between
resin and a matrix. Hardeners/catalysts (according to an increased activity) are
75% phosphoric acid (V) (for furan sands of a high urea content), p-toluenesul-
fonic acid (PTS), xylenesulfonic acid (XSA), and benzenesulfonic acid (KBS),
sometimes with addition of sulfuric acid (VI) (Table 6.1). XSA and KBS acids are
strong acids and are applied when short hardening time is required [1]. In all cases
water solutions of these acids are used. Sulfonic acids contain certain amounts of
alcohol. Sulfonic acids are causing corrosion of equipment, have unpleasant
smells, and sulfur contained in them unfavorably influences the surface structure
of cast iron castings with spheroidal or vermicular graphite. Therefore they are
partially substituted by, e.g., lactic acid (Table 6.1). A task of acidic catalysts is
neutralizing of alkaline contaminations contained in sand and the initiation and
maintaining the binder hardening process due to a condensation and lattice
forming.
A mixture of apple acid and ammonium sulfate significantly reduces the VOC
emission. Mixtures of strong organic acids, aromatic and aliphatic, due to which
50% decrease of the sulfur content was achieved, were also developed.
In order to increase the efficiency in casting production, the special activators to
speed up a polymerization of furfuryl alcohol are introduced.
Molding sands bound by furan resin-based binders are characterized by the
following advantages [3]:
• High dimensional accuracy of castings
• Possibility of making cores of complex shapes
• High heat strength and simultaneously the excellent knocking out ability
• Possibility of controlling the hardening rate
• Small amounts of binder additions
• Low energy consumption of the sand preparation
• Higher tensile strength of the given resin contents than of other molding sands
• Faster hardening of furan resin than other binders in the warm-box technology
Their drawbacks are:
• Relatively long hardening time
• Short life time
• Harmfulness of emitted gases
• Relatively high price (high price of furfuryl alcohol)
• Problems with storing of spent sands and after reclamation dusts
6.1 Furan Acid Catalyzed 147
Table 6.1 Hardeners used in molding sands with furan resins

Molecular Content
Name/chemical Structural weight Tmelting Tboiling of sulfur
formula formula (g/mol) (°C) (°C) (mas. %) Abbreviation
Benzenesulfonic 158.18 65 171 20.27 KBS
acid/C6H5SO3H
p-Toluenesulfonic 172.20 106 140 18.62 KPTS

acid/CH3C6H4SO3H
o-Toluenesulfonic 172.20 92 129 18.62 KOTS

acid/CH3C6H4SO3H
Xylene sulfonic 186.15 103 185 17.22 XSA

acid/C8H10O3S
Sulfuric acid/H2SO4 98.08 10.38 279.6 32.69 KS
Lactic acid C3H6O3 16.9 122
90.08 …… KM
53 103
Methanesulfonic 96.11 20 169 30 KMS
acid
CH3SO3H
• SO2 emission and organic aromatic substances, mainly benzene and furfuryl
alcohol, unfavorably influencing work conditions in foundries
• Application of acidic catalysts of corrosive properties
A molding sand is mixed with liquid resin and hardener at a room temperature.
A resin addition usually equals from 0.7% to 1.5% in relation to sand. The hard-
ener fraction constitutes 30–50% in relation to resin. Optimal hardening tempera-
ture equals 20–25 °C, but usually in practice, 15–30 °C are used. The temperature
decrease significantly prolongs the preliminary hardening time (necessity of longer
keeping a pattern in a mold), while higher temperatures reduce the forming time,
lower the sand fluidity, as well as increase emissions of solvents worsening the work
conditions [4]. High-silica sands of not high value of the acid demand are the best to
be applied as matrices, since this means that there is a small content of alkaline addi-
tions (a hardener first of all reacts with alkaline additions). Chromite sands can be also
applied (with certain exceptions, due to high pH (sometimes 9–10) of some kinds of
sands) and zirconium sands. On the other hand, the application of sands of an alkaline
character (e.g., olivine sand) is disadvantageous, considering higher uses of hardeners
and longer times of binding. Using sands of oval or globular grains is recommended.
Behavior of furan resin when it is polymerizing under a strong acid influence is
characteristic. At the beginning the molding sand is green, while after its total hard-
ening it changes into black color. This change of colors is caused by the formation
of chromophoric substances during individual hardening stages.
Molding sands with furan binders are characterized by a high dimensional accu-
racy and high resistance to casting defects on the metal/mold boundary. After the
metal solidification, they are easily decomposing, due to which castings can be eas-
ily knocked out. Molding sands with furan binders have also a high tensile strength
and excellent heat resistance due to which they are suitable for making snap flask
molds. They often operate at the sand/metal ratio, being 2:1. Molding sands hard-
ened by phosphoric acid (V) are more difficult for the mechanical reclamation than
molding sands hardened by sulfonic acids. In case of the given resin hardened by
phosphoric acid, higher values of a tensile strength are obtained than when stronger
sulfonic acid is used. Generally, the weaker acid and/or the slower catalyst, the
higher tensile strength values obtains the molding sand.
The hardening rate can be controlled either by the hardener type or by its amount,
at the assumption that sand is of the same kind and temperature (optimal t emperature:
20–30 °C) [5, 6]. Commercial furan resins are classified in dependence on the nitro-
gen and water content. The nitrogen content is from 0% to 8% while water content
from 0% to 30%. The lower nitrogen and water content in the resin the better resin.
Moreover, a low nitrogen content can be obtained only at high fractions of furfuryl
alcohol, i.e., in the most expensive resins [7].
Admittedly the alcohol content (the so-called free alcohol) in resin can reach
even 90% (high content of furfuryl alcohol lowers a resin viscosity and decreases a
nitrogen content), but – in accordance with the binding regulations – substances
containing above 25% of free furfuryl alcohol are treated as poisons and must be
properly marked.1 Therefore producers of these resins are limiting the furfuryl alco-
hol content applying its substitutes.
Generally, furan resins of a small and medium content of free furfuryl alcohol are
applied for cast iron and non-ferrous metals castings, while binders of a high con-
tent of free furfuryl alcohol and a small content of water and nitrogen are applied for
steel castings.
1
Ruling of the European Parliament and Council (WE) NR 1272/2008 of December 16, 2008,
concerning classifications, markings, and packings of substances and mixtures, changing and over-
ruling 67/548/EWG and 1999/45/WE Directives and changing the Ruling (WE) nr 1907/2006
(Official Journal UE L 353/2 from 31.12.2008).
The standard hardener for molding sands with furan resin contains PTS acid,
which under an influence of the liquid metal temperature is decomposing
(Fig. 6.1) [8].
According to the reaction in Fig. 6.1, the formed SO2 is adsorbing on the liquid
metal surface, where is decomposing, producing sulfur in an atomic form:
SO2 (g) = S + 2O

Sulfur atoms diffuse in liquid metal, causing sulfurization of the casting surface
layer. Sulfur can also react with Mn, Fe, and Mg forming molecules of the type (Fe,
Mn, Mg)S, which have relatively low melting temperatures.
The polymerization process of furan resin occurs according to the reaction
(Fig. 6.2):
Water plays a special function in molding sands with furan resins. There are a
few water sources in molding sands with furan resins:
• Water, which is formed in the polycondensation reaction of resin
• Water, which is introduced into molding sands as solvent of hardeners (water
solution of acids)
• Moisture content in sand matrices
• Water present in the atmosphere in a form of water vapor
The moisture presence causes a significant decrease of molding sand strength
and prolongs a preliminary hardening time, and in places where water is in contact
with resin, the binding process stops. Sands of a moisture content above 0.2% used
as a matrix significantly slow down the hardening process and decrease strength and
fluidity of a molding sand.
A sequence of introducing components into a mixer is important for obtaining
molding sands of optimal properties. First of all, hardener should be added to a sand
and well mixed. If resin would cover sand grains first, in places into which hardener
was introduced, its concentration would be very high. It means, that spaces of too
high hardener concentration and of much lower strength would be in the molding
Fig. 6.1 Thermal decomposition of p-toluenesulfonic acid [8]

Fig. 6.2 Polymerization reaction of furan resin
sand. Hardener and resin should never be simultaneously introduced into the mixer,
since between them occurs strongly exothermic reaction. When hardener is in
excess, brittle and weaker bonds are formed, and resin changes its color into black,
and stripes resembling salt and pepper grains occur. This effect occurs the most
often when hot sands are applied or the mixing intensity is too small or when the
mixer does not operate properly.
It was found that resin hardened by weak phosphoric acid obtains higher tensile
strength values than when it was hardened by stronger sulfonic acid. Generally, the
weaker hardener, the higher tensile strength of a molding sand. The work time of a
molding sand with furan resin equals usually 50–60% of its strip time [9]. Water as
well as alcohol protective coatings can be applied for molds and cores made of
molding sands with furan resin. Molding sands with furan resin, after 3 hours of
removing the pattern from a mold, achieve 70–90% of their final properties.
Therefore protective coatings can be deposited only after 1–3 hours, after a pattern
was taken out from a mold. Another reason of the later coating placement (espe-
cially water based coatings) is water emission (as a side product) in the resin hard-
ening reaction. This water has to leave a mold or core before it will be fully
hardened. Water slows down the hardening process and causes that molding sands
are hardened “from outside into the depth,” which means that the layer with depos-
ited coating – which is exposed to the air influence – is hardening earlier than the
molding sand in the subsurface layer. Therefore the control of the molding sand
hardening should be performed in layers situated deeper from the mold (core)
surface.
A temperature, which should be monitored and maintained at a constant level, is
important in this technology. The optimal temperature should be 20–30 °C. The
hardening rate increases with temperature increases and slows down when the tem-
perature decreases. By the application of a catalyst, the hardening rate can be also
influenced.
In order to improve a binding ability of binders, modifiers are used. The most
often silanes are used as modifiers, since their addition increases strength and
improves resistance to a moisture content. Their influence is based on increasing the
binding ability between inorganic surfaces of sand grains and the organic binder.
Due to a silane influence, the resin addition can be decreased while maintaining the
same level of the molding sand strength. The silane addition equals 0.3–0.5%.
Furan resins based binders under an influence of the liquid metal temperature are
subjected to destruction, due to which the sand knocking out can be easily per-
formed, especially at making castings of iron alloys.
The moisture presence in a molding sand causes dilutions of the acidic catalyst
and slowing down the hardening reaction. It should be remembered that water is the
side product of the resin hardening reaction and certain waiting time is needed to
allow evaporation of this water from a mold. Furan sands can be either formed in
molding boxes or without them. In case of steel castings of a weight of 1 Mg and
above, they are – in principle – formed in flask mold, due to the safety of employees.
Smaller castings can be formed in flask less mold.
Atmosphere Changes in a Mold
A coarse-grained microstructure of a casting has a disadvantageous influence on
mechanical properties of produced castings. The degree of fineness of the casting
structure mainly depends on the casting cooling rate. The heat abstraction rate from
a casting to a sand mold – expressed as a thermal conductivity of a mold – depends
on the kind of matrix and on binder grain sizes, inter-granular spaces, kinds of gases
inside these spaces, and the mold temperature. One of parameters, which can be
controlled and thus influence the mold thermal conductivity, is the kind of gases
present in inter-granular spaces [10]. When a mold is filled with gas of a higher
thermal conductivity than the air, e.g., helium which in the temperature range
25–500 °C has five times higher thermal conductivity than air, the cooling rate sig-
nificantly increases causing the higher microstructure refinement and significant
improvements of casting mechanical properties. According to Doutre D [11, 12],
filling the mold with helium, instead of air, shortens cooling castings by 30–50%
(which results in the tensile strength increasing by 22%) and the apparent creep
limit by 34%, without worsening plasticity.
Reclamation of Spent Molding Sands
Spent molding sands (SMS) with furan resin can be subjected to the thermal as well
as mechanical reclamation. It is possible to apply the matrix containing 90% of the
mechanically reclaimed material as well as the matrix containing 100% of the
reclaimed material obtained in the thermal or thermal-mechanical reclamation pro-
cess. The assessment of the reclaim quality contains determinations of loss on igni-
tion, gas evolution rates, acid demands, nitrogen and sulfur content, and pH values
[3]. The determination of nitrogen is necessary, especially in case when resins con-
taining urea are applied. Nitrogen allowable contents depend on the destination of
molding sands prepared with the reclaim fraction and are equal [3] for gray cast
iron, 0.15%; high-quality cast iron, 0.1%; spheroidal cast iron, 0.1%; alloy cast iron,
0.01%; and cast steel, 0.01%. Allowable losses on ignition (LOI) and gas evolution
rates also depend on the alloy for which the reclaim-based molding sand is intended
for cast iron LOI, 2.5–3.5%, and gas evolution rate max. 20 cm3/g while for cast
steel LOI, max. 2.2% and gas evolution rate max. 10 cm3/g. The kind of the applied
hardener also influences the reclaim quality. Using of phosphoric acid (V) causes a
gradual increase of phosphates presence in a molding sand, which can unfavorably
influence the reclaim refractoriness.
In case, when sulfonic acids are applied as hardeners, in successive reclamation

cycles the sulfur content in molding sands grows. This can be the reason of defects
in castings of cast iron alloys, especially of spheroidal and vermicular cast iron, as
well as can cause a significant SO2 emission during molds pouring with liquid alloy.
When the reclaim, originated from the mechanical reclamation, is applied as a
matrix the amount of added resin can be decreased. The sulfur content should not
exceed 0.15%.
Due to a high tendency of sulfur and nitrogen for cumulating in the sand, the
limitation of these elements in the binder causes their decrease in spent sands and
then in a reclaim. The influence of S and N content in a binder on these elements
level in the reclaim obtained from the mechanical reclamation process is presented
in Figs. 6.3 and 6.4 [13].
The sulfur and nitrogen reduction in a binder has the advantageous influence not
only on work conditions in foundry plants but also on the molding sand quality. The
sulfur content decrease in the sand from app. 0.1% to 0.07% contributed to lowering
SO2 concentration in gases and to limiting the sulfur negative influence on the cast-
ings quality. The nitrogen content decrease from 0.13% to 0.07% limits the risk of
pinholes formations on casting surfaces.
Fig. 6.3 Influence of a sulfur content in a binder on its amount in a reclaim: (red line, low-sulfur
binder; black line, high-sulfur binder). (Reprinted by permission from Ref. [13])
Fig. 6.4 Influence of nitrogen content in a binder on its amount in a reclaim: (red line, low-
nitrogen binder; black line, high-nitrogen binder). (Reprinted by permission from Ref. [13])
Thermal Decomposition of a Binder

On account of a very high temperature of liquid metal, the pyrolysis process of
molding sands with furan resin-based binders occurs nearly completely at the
boundary: metal molding/core sand (it is the so-called flash pyrolysis). At a further
distance from this boundary as the warm front is shifting, only a partial decomposi-
tion of molding sand will occur (slow pyrolysis). For furan resins, the sum of
generated HAPs in the flash pyrolysis process was approximately 40% higher than
in the slow pyrolysis [14]. During the slow pyrolysis, several processes occur. On
the TG curve the highest weight loss occurred at temperatures up to 300 °C and was
mainly caused by water evaporation and carbon dioxide emission.2 The HAP emis-
sion was negligible. Starting from a temperature of 300 °C, the emission of sub-
stances from the BTEX group and monomers of methylfurans (2-methylfuran and
2.5-methylfuran) grows, which indicates that bonds in the hardened binder structure
are cracking. The main HAP amount was liberating within the temperature range
300–700 °C, when the furan-based binder was slowly heated.
During the flash pyrolysis (heating time up to a temperature of 920 °C equals
0.2 s) such reactions as opening of the furan ring, cracking of carbon bridges, and
further decomposition of chains fragments occur nearly simultaneously. A rapid
binder heating causes cracking of its structure and releasing large amounts of vari-
ous substances in a short time.
The authors assumed that the main source of the HAP emission (where xylenes
dominate), during the thermal decomposition of the furan-based binder, was xylene-
sulfonic acid, applied as a hardener. This conclusion complies with results obtained
by Dungan et al. [15] in case of pyrolysis of furan binder hardened by toluenesul-
fonic acid. Phenol was the dominating component in the emitted HAP gases, while
substances from the BTEX group were either negligible or below the detection limit.
Wang et al. [14] proposed the thermal decomposition pathways of the furan
binder. They assumed that the structure of hardened furan resin consisted of
branched and hardened heterocyclic and aromatic rings. During a uniform heating,
the furan binder cross-linked structure gradually decomposes, and volatile sub-
stances are releasing. At a temperature of app. 150 °C starts the SO2 emission, since
R-SO2OH bond is relatively weak. Furan rings in a polymer are gradually decom-
posing in the temperature range, 100–500 °C, and disappearing at higher tempera-
tures. Ring opening generates chain fragments, which can further decompose.
Oxygen present in chain fragments is removed at the beginning of heating in a form
of water or carbon oxides, and therefore carbon chains are broken into shorter ele-
ments forming alkenes (CnH2n) or alkynes (CnH2n-2). On the other hand, at tempera-
tures above 300 °C unsaturated hydrocarbons: C3H6, C4H6, and C5H8 are subjected
to changes, because carbon skeletons require higher energy for tearing. Starting
from a temperature above 300 °C, a noticeable emission of toluene, xylenes,
2-methylfuran, and 2.5-dimethylfuran is visible. This indicates that aliphatic
bridges joining furan and aromatic rings are breaking, which leads to the emission
2
In case when in TGA/MS investigations nitrogen is applied as a carrier gas, CO is not identified
by mass spectroscopy method, because their molecules can not be distinguished (m/z = 28).
of methyl derivatives of furan and benzene. Methyl furan derivatives are thermally
unstable at high temperatures and were further decomposed into products similar to
chain fragments (Fig. 6.5).
Investigations of Acharya et al. [19] of furan resins hardened by p-toluene sul-
fonic acid, performed by the thermogravimetric method, indicated that weight
losses within the temperature range 150–700 °C were caused by the emission of
various gases generated due to the furan ring decomposition. Furan, toluene, ethyl-
benzene, styrene, phthalic acid (benzene-1,2-dicarboxylic acid), palmitic acid
(hexadecanoic acid), and thiophene are the main gases. Benzene constituted more
than 50% fraction in emitted gases.
Fig. 6.5 Overlay reaction pathways for the formation of aromatic compounds in pyrolysis of the
furan binder cured with p-xylene sulfonic acid. (Adapted from Refs. [16–18])
The furan resin pyrolysis at the temperature of 750 °C generated 12 furan-based

substances of a molecular mass from 96 (dimethylfuran) to 242 (2,2′-2(-furylmeth-
ylene)bis(5-methylfuran). The highest fraction had 2-(2-furanylmethyl)-5-
methylfuran and 2,2′-methylenebis (5-methylfuran). The example of the hardened
furan resin structure is shown in Fig. 6.5. The formation of such compounds as
2,5-dimethylfuran and 2,3,5-trimethylfuran suggests that during the thermal decom-
position of furan resin breaking of methylene bridges (−CH2−) between furan rings
occurs. Broken methylene bridges of furan resin are forming groups of free radicals,
which by joining with hydrogen are forming methylfurans [15, 20].
Since in the composition of gases emitted from the binder – containing furan
resin hardened by xylenesulfonic acid – xylenes were dominating, Wang et al. [18,
21] assumed that the main source of the HAP emission is a hardener. This is con-
firmed by investigations of Dungan [15] and M. Holtzer [22–24], who performed
pyrolysis of binders containing furan resin hardened by p-toluenesulfonic acid. In
gases – generated as the result of this binder pyrolysis – the main component from
the HAP group was phenol, while the BTEX group emission was negligible or not
identified. It means that the hardener is decisive in the kind and amount of emitted
HAP during the furan binder pyrolysis. Therefore in order to limit the emission of
hazardous substances, more friendly hardeners should be developed. These could
be, e.g., arylsulfonic acids.
Ar − H + HO − SO3 H → Ar − SO3 H + H 2 O ( sulfur is not released )

Schematic presentation of the pyrolysis of binder with furan resin hardened by
p-xylenesulfonic acid and formation of aromatic substances from the HAP group is
shown in Fig. 6.6.
Investigations concerning the emission of substances from the BTEX and PAH
groups during the thermal decomposition of molding sands with furan resin were
performed by M. Holtzer’s team, under laboratory as well as semitechnical condi-
tions [25–29]. Investigations performed at the temperature range 500–1300 °C as a
flash pyrolysis indicated that for each compound from the BTEX group, it is pos-
sible to determine the temperature range at which its emission is the highest [16].
The free furfuryl alcohol content within the range 25–72% did not have – in prac-
tice – any influence on the PAH emission, which was equal app. 10–11 mg/kg of
sand. For resins of a lower content of free furfuryl alcohol, naphthalene was the
main compound from the PAH group. On the other hand, the hardener influence
(sulfonic acids) was noticeable. Partial substitution of p-toluenesulfonic acid (65%
water solution) by lactic acid (36–41% water solution of p-toluenesulfonic acid
+30–33% water solution of lactic acid) caused the PAH emission reduction by app.
30%. When phosphoric acid (V) was applied as a hardener, the HAP emission was
app. 3 mg/kg of sand, while it was 10 mg/kg when PTS acid was applied [25, 28].
However in the compounds of the BTEX group, neither the substitution in the
hardener a part of PTS acid by lactic acid, nor free furfuryl alcohol content in resin
had any influence on the emission of these compounds. This emission was at the
Fig. 6.6 Scheme formation of aromatic compounds from the PAHs group by pyrolysis process
(Reprinted by perrmission from Ref. [17])
Hydrogen–abstraction/acetylene–addition (HACA) mechanism accelerate the formation polycy-
clic aromatic hydrocarbons (PAHs) like pyren from naphthalene
level 560–660 mg/kg of sand. The main, and in practice the only one, compound
emitted in all experiments was benzene (the benzene fraction in the BTEX group
was nearly 99%) (Table 6.2).
Holtzer et al. [25, 26] investigated the effect of free furfuryl alcohol in furan resin
on PAHs emissions (Table 6.3).
The total emission of compounds from the HAP group is, in practice, the same
(within the error limit) for all tested resins. Certain differences occur in the compo-
sition of the emitted gases, e.g., the lower content of free furfuryl alcohol in resin the
higher concentration of naphthalene in emitted gases. Taking into account the carci-
nogenic influence of benzo(a)pyrene, decreasing of its emission when the free fur-
furyl alcohol content in resin is decreased is a positive fact. Tiedje N. et al. [30] were
Table 6.2 Emission of compounds of the BTEX and HAP groups from molding sands with furan
resin (containing 25% of free furfuryl alcohol) hardened by various hardeners (the sand sample
was poured with cast iron of a temperature of 1350 °C)
Hardener
Parameter WS NS
Concentration (mg/kg molding sand)
Content of BTEX Benzene 627.0 Benzene 654.5
Toluene 18.3 Toluene 10.1
Ethylbenzene b.l.d. Ethylbenzene 0.6
Xylenes b.l.d. Xylenes 1.2
Total 645.3 Total 665.2
Content of HAPs 10.411 6.870
WS, 65% aqueous solution of p-toluenesulfonic acid; NS, mixture of 36–41% aqueous solution of
p-toluenesulfonic acid +30–35% aqueous solution of lactic acid; b.l.d., below the limit of detection
Table 6.3 Concentration of PAHs which released during the thermal decomposition of molding
sands with furan resin with different contents of free furfuryl alcohol
Concentration PAH (mg/kg) Concentration PAH (mg/ kg)
molding sand molding sand
Compound A B C Compound A B C
Naphthalene 0.609 2.400 5.420 Benzo (b) 0.747 0.399 0.220
fluoranthene
Acenaphthene 0.012 0 0 Benzo (k) 0.244 0.120 0.280
fluoranthene
Fluorene 0.212 0.083 0.180 Benzo (a) pyrene 0.712 0.650 0.210
Phenanthrene 0.856 0.512 0.590 Indeno (1,2,3-cd) 0.916 0.571 0.180
pyrene
Anthracene 0.333 0.144 0.190 Dibenzo (ah) 0.006 0.000 0.220
anthracene
Fluoranthene 2.808 2.154 0.800 Benzo (ghi) 0.472 0.350 0.060
perylene
Pyrene 2.084 1.759 1.950 Benzo(a) 0.428 0.209 1.230
anthracene
Chrysene 0.441 0.473 0.100 Total PAHs 10.940 9.914 11.640
± ± ±
2.188 1.983 2.328
Mold pouring with cast iron at 1350 °C, free furfuryl alcohol content A, 71–72%; B, 50%; C,
23.5–24.75%
testing the temperature influence on the composition of gases emitted during the
pyrolysis of the molding sand with furan resin under semi-technical conditions
(experimental mold). In order to differentiate temperatures, the mold was poured
with cast iron (1400–1420 °C), bronze (1180–1200 °C), and aluminum alloy
(700–720 °C). Furan resin of 50–55% of free furfuryl alcohol, free phenol <1%, and
free formaldehyde 0.2–0.5% was hardened by p-toluenesulfonic acid (PTS) and
benzenosulfonic (BS). The obtained results are listed in Table 6.4.
Table 6.4 Analyses of gases emitted from molds made of molding sands with furan resin hardened
by sulfonic acids
Emissions of gases, mg/per kg molding sands
Group of compounds Liquid metal/hardener Fe + PTS Cu + PTS Al + PTS Fe + BS
Aromatic Benzene 32.9 17 1.2 78
hydrocarbons
Toluene 61.1 66 27.8 6.1
Xylenes + ethylbenzene 1.8 1.9 0.4 0.4
Other aromatic 0.2 1.1 1.2 0
hydrocarbons
Total of aromatic 98 86 30.6 84.5
hydrocarbons
Phenols Phenol 0.1 3.7 0.1 1.4
Cresol o, m, p 0.3 1.4 0 1.2
Xylenol 0 0.9 0 0.3
Total of phenols 0.3 6 0.1 2.9
Aldehydes Formaldehyde 0.4 0.4 0.2 0.2
Acetaldehyde 0.4 0.3 0.2 0.3
Acrolein 0 0 0 0
Acetone 2.3 2.2 1.7 2.6
Propanol 0 0.05 0 0
2-Butanone 0.2 0.2 0.1 0.2
Butanal 0 0 0 0
Benzoic benzoate 0.1 0.2 0 0
Pentanal 0 0 0 0
Hexanal 0 0 0 0
2-Hydroxy benzoic aldehyde 3.3 0 0 3.2
Total of aldehydes 6.7 3.35 2.2 6.5
Total CO 487 65 24.2 258
Fe + PTS – FA binder cured with p-toluene sulfonic acid (PTS). Cast iron pouring at 1350 °C
Cu + PTS – Bronze pouring at 1200 °C
Al + PTS –Aluminum alloy pouring at 700 °C
Fe + BS – FA binder cured with benzenesulfonic acid (BS). Cast iron pouring at 1350 °C
The temperature influence on the amount and composition of the gases emitted
from the aromatic hydrocarbons was very visible at the temperature range
700–1200 °C. This concerned specially toluene, the emission of which from the
mold poured by Al alloy was two times lower than from the mold poured by bronze
or cast iron. For aldehyde emission, the temperature influence is smaller. However,
the largest differentiation occurred in case of CO, which emission from the mold
poured with cast iron was nearly ten times larger than from the mold poured by
bronze. Probably this was mainly caused by a high carbon content in cast iron, not
by the temperature (which difference was approximately 200 °C). When BS acid
instead of PTS acid was applied as a hardener the CO emission was nearly twice
smaller in case of iron casting. Moreover, from the binder hardened by PTS acid,
mainly toluene is emitted while from the binder hardened by BS acid mainly benzene.
In case of furan resins a serious ecological problem constitutes SO2 and nitrogen
oxide emissions as well as unpleasant smells, especially in workplaces. The recently
developed new furan resins (more reactive, free formaldehyde content <0.1%, small
nitrogen content) and new hardeners (of a reduced sulfur and aromatic compounds
content) allow for a significant decrease of these contaminations emissions as well
as of the unpleasant smells level.
The application of the reclaim – obtained as the result of the mechanical recla-
mation of sands with furfuryl resin – as a matrix significantly increases amounts of
emitted compounds from the BTEX (Table 6.5) and HAPs (Table 6.6) group. When
fresh sand used as a matrix was substituted by the reclaim, the volume of emitted
gases increased twice and the benzene amount three times. Also the total amount of
Table 6.5 Emission of BTEX gases from molding sands made on matrices with various fractions
of the reclaim (100SP, matrix, 100% of fresh sand; 50SP50R, 50% of fresh sand +50% of reclaim;
100R, matrix, 100% of reclaim) (sand composition: urea–formaldehyde resin modified by furfuryl
alcohol, 1.0%; hardener, 0.5%)
Emission of BTEX gases
Volume of gases (mg/g resin)
Sample (dm3/g resin) B T E X
100 SP 1.280 33.312 0.283 0.062 0
50SP50R 1.826 51.252 1.815 0 0
100R 2.437 95.660 9.114 0.118 0.772
Reprinted by permission from Refs. [31, 32]
B benzene, T toluene, E ethylbenzene, X xylenes
Table 6.6 Emission of PAHs from molding sands made on matrices with various fractions of the
reclaim
Concentration PAHs Concentration PAHs (μg/g
(μg/g resin) resin)
Compound 100SP 50SP50R 100R Compound 100SP 50SP50R 100R
Naphthalene 312.12 511,91 1018,16 Benzo (b) 49.23 74.81 18.32
fluoranthene
Acenaphthene 0.48 0.47 1.38 Benzo (k) 18.68 25.35 7.30
fluoranthene
Fluorene 8.09 9.91 89.69 Benzo (a) pyrene 80.47 103.89 23.22
Phenanthrene 3.72 46.04 84.77 Indeno (1,2,3-cd) 47.81 82.52 15.87
pyrene
Anthracene 14.25 16.89 32.45 Dibenzo (ah) 8.24 2.30 2.55
anthracene
Fluoranthene 84.41 185.03 94.83 Benzo (ghi) 35.76 47.56 13.20
perylene
Pyrene 5893 147.51 70.51 Benzo(a)anthracene 25.71 39.99 17.23
Chrysene 14.39 14.39 8.83 Total PAHs 795.82 1330.58 1498.35
± ± ±
159.16 266.12 299.67
emitted HAPs increased twice. It was mainly caused by the increased amount of
naphthalene, which in case of a molding sand on fresh sand matrix constituted 40%
while when the reclaim was the matrix 70%.
Leaching of Harmful Substances from Spent Molding Sands into the
Environment
The second important element of assessing the influence on the environment of the
given technology of molding and core sands is a tendency of these sands for eluting
hazardous substances.
Ji et al. [1] investigated elution (extraction by dichloromethane) of organic sub-
stances, including HAPs and metals, from the knocked out sands with furan resin
hardened by acids. Molds were poured by cast iron, cast steel, and aluminum alloys.
The largest HAP amount (0.68 mg/kg of sand) was eluted from sands originated
from molds in which iron castings were made. From sands originated from molds in
which steel castings (0.22 mg/kg of sand) and aluminum castings (0.24 mg/kg of
sand) were made, nearly three times less HAPs was eluted. In practice, regardless of
the casting alloy, approximately 30% of analyzed HAPs constituted naphthalene.
Concentrations of remaining organic compounds (benzyl aldehyde, benzyl alcohol,
sulfonic derivatives, esters of dicarboxylic acids, glycol derivatives, and hydrocar-
bons) eluted from molds in which castings of various alloys were made were equal
0.2–0.4 mg/kg of sand.
Metals concentrations in filtrates obtained during leaching of spent sands were
small and equal – in total (for 9 determined metals: As, Ba, Cd, Cr, Pb, Se, Ag, Cu,
Zn) – for iron castings 0.092 mg/dm3, for steel castings 0.583 mg/dm3, and 0.105 mg/
dm3 for sands originated from aluminum alloy castings (not taking into account Cu,
which is an alloying component). Metals have a tendency of accumulation in mold-
ing sands in successive cycles. Holtzer et al. [27] were testing leaching of sub-
stances from sands bound by furan resin (free furfuryl alcohol content in resin was
<25%) hardened by paratoluenesulfonic acid, prepared on the high-silica matrix
and the reclaim obtained from the mechanical reclamation process. Castings were
made in molds of molding sands containing various amounts of reclaim as the
matrix component: 100% of high-silica sand, 50% of high-silica sand, and 50% of
a reclaim and 100% of a reclaim. After each casting knocking out the sand was
subjected to leaching tests.
Concentrations of eluted substances were growing after successive reclamation
cycles and with an increase of the reclaim fraction in the molding sand (Table 6.7).
When 50% of high-silica sand was substituted by a reclaim, the BTEX concentra-
tion in filtrates was three times increased. The total concentration of PAHs was (in
filtrates) very small and equaled <0.10 mg/kg of sand (or <0.01 mg/dm3) for all
tested sands.
At present, investigations concerning furan-based binders are being developed in
two directions [33–35]:
• Hardener modifications leading to:
–– The reduction of sulfur content (e.g., by the improved elimination of sulfonic
acids), which will decrease SO2 emission and thus will limit the harmfulness
Table 6.7 Effect of reclaim addition on leaching of substances from molding sand with furan
resin
Molding sand
Parameter Unit 100PS 50PS50R 100R
Arsenic mg/kg ds 0.018 0.102 0.019
Barium mg/kg ds 1.84 1.46 0.584
Cadmium mg/kg ds 0.029 0.044 0.022
Chromium – total mg/kg ds <0.030 0.089 0.240
Copper mg/kg ds 0.143 0.306 0.525
Mercury mg/kg ds <0.005 <0.005 0.0060
Molybdenum mg/kg ds <0.040 <0.040 <0.040
Nickel mg/kg ds 0.361 0.533 0.560
Lead mg/kg ds 0.150 0.604 1.23
Antimony mg/kg ds <0.010 <0.010 <0.010
Selenium mg/kg ds <0.010 <0.010 <0.010
Zinc mg/kg ds 4.39 5.31 3.28
Chlorides mg/kg ds <20 <20 <20
Fluorides mg/kg ds <1.0 <1.0 <1.0
Sulfates mg/kg ds 51 100 83
Phenolic index mg/kg ds 0.31 0.30 0.24
Dissolved organic carbon (DOC) mg/kg ds 1610 2420 3120
Total dissolved solids (TDS) mg/kg ds 3780 5920 7160
pH 4.4 4.1 3.1
Total organic carbon (TOC) mg/kg ds 7400 13100 20000
Benzene, toluene, ethylbenzene, xylenes – total (BTEX) mg/kg ds 0.19 0.70 0.60
Polychlorinated biphenyls – total (PCB) mg/kg ds <0.020 <0.020 <0.020
Mineral oil (C10 – C40) mg/kg ds 9.17 12.1 11.3
Polycyclic aromatic hydrocarbons – total (PAHs) mg/kg ds <0.10 <0.10 <0.10
Water content % <0.5 <0.5 <0.5
100PS 100% fresh sand, 50PS50R 50% fresh sand and 50% reclaim, 100R 100% reclaim, ds dry
sample
of this technology as well as will limit the degradation of spheroidal and ver-
micular graphite in castings surface layers
–– The limitation of evolving aromatic compounds amounts
• Resin modification, which contains:
–– Limitation of the free furfuryl alcohol content to <25%, at maintaining com-
parable properties of molding sands
–– Increase of resin reactivity, which will allow to decrease the added hardener
amounts
–– Reduction of the formaldehyde content, to improve work conditions
–– Reduction of the nitrogen content, even to the zero level, to eliminate gaseous
defects such as pinholes and to limit the nitrogen oxides (NOx) emission
6.2 Phenolic–Urethane No-Bake System (PUNB)
Molding sands bound by phenolic–urethane (PU) binder can be classified in depen-

dence of the state of aggregation of a catalyst, or as self-setting, phenolic–urethane
no-bake (PUNB) or hardened by gases phenolic–urethane cold-box (PUCB). The
binding mechanism of both molding sands is similar. The only difference is such
that in the cold-box system, gaseous amine is a catalyst which is blown through the
cold-box and the sand hardening occurs immediately, while in the self-setting sands
system, liquid amine is applied, which causes slowing the hardening process and
prolongation of the sand work time. The main reason of a wide application of these
molding sands is their thermal stability at high temperatures as well as a high pro-
duction efficiency. These sands were introduced into foundry in 1970 years. The
binder applied in this process consists of three components: solution of phenol–
formaldehyde resin (component 1), solution of diisocyanate (component 2) and ter-
tiary amine in liquid state (component 3) (Fig. 6.7). The binder hardening process
occurs as the result of phenol–formaldehyde resin reaction with isocyanate, in the
presence of the catalyst (amine).
Molding sands with cold-hardened phenol–urethane binder are not applied, in
practice, in Europe (in a small degree only in Germany), while in the USA, they
constitute 25% of all technologies of chemically bound sands. Foundry plants in the
USA are using more than 45,000 tonnes of these binders annually [36]. Molding
sands with phenol–urethane binder are characterized by a high strength at a small
resin addition, are hardening fast, and allow to apply a high reclaim fraction as well
as they have an excellent ratio of work time/strip time (above 60%), while for the
comparable binder hardened by acids, this value is below 30%.
Phenol resin as well as polyisocyanate are dissolving in organic solvents due to
their high viscosity. The selection of the proper solvent is very important in this
technology, since it decides on the rate and on the whole resin hardening process.
Liquid Part I + Liquid Part II Solid Binder
Amine
Phenolic + Polyisocyanate Urethane
Catalyst
Resin
O H
Amine O C N
OH + NCO Catalyst
Urethane bond
Solvent Solvent
Fig. 6.7 Structure of phenol–urethane binder

6.2 Phenolic–Urethane No-Bake System (PUNB) 163
Traditional solvents contain substances from the PAHs group of high boiling points.
They significantly contribute to the emission from cores, which occurs during the
mold pouring with liquid metal.
Typical average binder compositions are 0.5–0.8% of resin and 0.5–0.8% of
diisocyanate. Optimal sand temperature is 25–30 °C. A catalyst (amine) addition
equals app. 12% versus resin amounts. Under these conditions molding sand achieves
the compression strength of app. 4000 kPa. Due to the fact that component 2 of a
binder contains app. 11% of nitrogen, there is a risk of gaseous defects in steel cast-
ings. There is also a possibility of defects related to lustrous carbon (in iron castings)
and erosion effect due to a small initial strength of a molding sand at high tempera-
tures. An addition of 1–2% of ferrous oxide (Fe2O3) significantly reduces these nega-
tive effects. Molding sands with phenol–urethane binder are well reclaimed by the
mechanical reclamation, and the application of 90% addition of a reclaim is possible.
Defects of this technology are low strength of the molding sand at high tempera-
tures, difficulties with dismounting a mold, intensive smell of a solvent and catalyst,
and fumes generated during a mold pouring. In order to counteract main defects,
binders of small emissivity of fumes were developed.
Since viscosities of resin and polyisocyanate are too high to allow a binder to
cover efficiently matrix grains, application of solvents is necessary. Aromatic hydro-
carbons of high boiling points were typical solvents. However, these hydrocarbons
were the source of unpleasant smells, emission of VOC and HAPs during the core
preparation, pouring, cooling, and mold knocking out. Therefore new solvents,
which do not contain heavy aromatic hydrocarbons but are based on methyl esters
of vegetable oils, were developed. Methyl esters have high boiling points and appro-
priately small viscosity.
Biourethane Binders
In the traditional technology component (1) of a binder is based on phenol and
formaldehyde, which contain hazardous substances (HAPs). To limit harmful influ-
ences of this technology, at the end of 1990, this phenol–formaldehyde resin was
substituted by biourethane binder, more friendly, containing sugars (e.g., from
starch syrup) and humic acids (which occur in brown coal) soluble in vegetable
solvents. These both components have several alcohol groups, which can react with
isocyanate. Along with the improvement of work conditions and smaller emissions
of harmful substances, properties of a molding sand were also improved. Biourethane
binder at a room temperature indicated comparable or better properties than phe-
nol–urethane binder. Better properties, higher strength, stiffness, resistance to hot
distortion, and a smaller tendency of cores to becoming deformed. Molding sands
with biourethane binder had also better knocking out abilities and were more
environment-friendly than binders with traditional solvents (aromatic hydrocar-
bons). Biourethane binders can be also applied for producing castings of aluminum,
brass, gray, and spheroidal cast iron alloys and cast steel.
Molding Sands with Urethane Binder: PUROLiTe Process
This is a technology of molding sands cold hardened, intended for production of
molds and cores, being a version of the PUNB technology, which is characterized
by less arduous work conditions in casting houses and by lower environment pollu-
tion. Admittedly binders of both technologies are based on polyurethane, but differ
in their chemical composition and in thermal decomposition products (Fig. 6.8).
In the PUROLiTe technology, instead of phenol–formaldehyde resin applied in
the PUNB technology, polyoils based on polyethers ended with hydroxyl groups3
are used. These are macromolecular or oligomeric compounds built mainly of
chains containing ether bonds −R−O−, where R is composed of at least two methy-
lene groups and of an aromatic or aliphatic ring. Polyether reacts with isocyanate
forming urethane bond.
The PUROLiTe binder does not contain phenol, formaldehyde, and aromatic
hydrocarbons. Solvents do not contain aromatic compounds. During the mold and
core production, less unpleasant smells are emitted than in the traditional polyure-
thane technology [37].
The PUROLiTe binder consists of two basic components (esters of fatty acids
and carboxylic acid are solvents):
• Resin, which contains 70–85% of polyether of polyhydroxy alcohol, 5–10% of
short chain dialcohol, 10–20% of carboxylic acid ester
• Activator (isocyanate) contains 80–90% of MDI-oligomer, 10–20% of carbox-
ylic acid ester
Environment Influence of Molding Sands with Phenol–Urethane Binder
Wang C. et al. [38] and Zhao X. et al. [39] applied TG/DSC and FTIR method for
investigating the thermal decomposition of phenol–urethane binder. In the paralysis
process course – performed under not isothermal conditions – three stages can be
separated; however temperature ranges determined by individual authors were
slightly different. In stage I, at temperatures of up to 215 °C, an endothermic evapo-
ration of low-boiling solvents (applied for resin) and moisture emission occurred
and the thermal decomposition of binder started. In this temperature ranges were
evolving: carbon dioxide (CO2), ammonia (NH4), methane (CH4), ethane (C2H5),
and carbon oxide (CO). Stage II, in the temperature range of 215–315 °C, had a
Fig. 6.8 Differences in structures of binders applied in the PUNB and PUROLiTe technology.
(Reprinted by permission from Ref. [37])
3
Generally polyurethanes are obtained by polyaddition of di- or triisocyanate with substances
containing free hydroxide groups (−OH) of polyoil type (polyesters or polyethers).
character of a low-temperature paralysis, in which apart from the same gases as in

stage I nitrogen oxide (NO) was additionally evolving. Stage III, which occurred in
the temperature range of 315–432 °C, was identified as responsible for regroupings
in the structure of phenol–urethane binder or for possible decompositions of binder
particles into aromatic benzene derivatives (bonds joining aromatic rings with
methylene bridges (−CH2−) in resins are breaking). This happens within the tem-
perature range 320–420 °C. It is an exothermic reaction. Simultaneously the inten-
sity of peaks, corresponding to substances containing nitrogen (e.g., NH3 and NO),
was growing. This means that C–N bonds were nearly completely broken, and the
molding sand strength drastically decreased. Similar results obtained Giese S.R. et al.
[36]. Zhao X. et al. [40] calculated, on the bases of the Arrhenius equation, the acti-
vation energy of stages II and III. The activation energy of stage II (low-temperature
paralysis) was 60.8 kJ/mol while of stage III (high-temperature paralysis)
233.7 kJ/mol.
Investigations concerning the emission of gases during such operations as pour-
ing, cooling, and casting knocking out indicated that approximately 80% of HAPs
and VOCs is emitted at castings knocking out from molds.
Giese and Shepard [41] tested an influence of the atmosphere character on ther-
mal decomposition products of phenol–urethane binder. Mass losses on TGA curves
were identical for samples tested in the neutral nitrogen atmosphere as well as in the
reducing atmosphere containing 20% of carbon oxide +80% of nitrogen. The final
mass constituted 28% of the initial mass of the sample, and this was carbon. A com-
bustion of phenol–urethane binder was not complete in these atmospheres, and
mass losses were the effect of a binder decomposition into VOC, gaseous hydrocar-
bons, and light gases. During the stage I compounds of heavier molecules were
formed: cresols, xylenes, phenol, toluene, naphthalene, and its derivatives. At fur-
ther stages, molecules of a large molecular weight were breaking into molecules of
a small weight, such as methyl oleate (C17H33COOCH3), dimethyl adypinate
(C4H8(COOCH3)2), methyl esters, and benzene, and – in addition – lighter gases,
CO, CO2, and H2, were formed. Cory A. Lytle et al. [42] found that the VOC amount
(among others HCN, CH4, CO) increases, when the pyrolysis temperature increases.
Admittedly, the kind of the atmosphere did not have the influence on the total mass
loss of a sample, but it had a high influence on the temperature range at which HAP
and VOC were formed. The highest amount of these compounds is generated in a
neutral (e.g., nitrogen) atmosphere. In reducing and oxidizing atmospheres, the
amount of HAP and VOC is decreasing, while the emission of light gases such as
hydrogen, propane, and water vapor increases. In case of a reducing atmosphere, the
temperature range of forming HAP and VOC shifts to higher temperatures as
compared with an oxidizing atmosphere, without changes of amounts.
TGA curves obtained for samples tested in the atmosphere containing 20% of
oxygen +80% of nitrogen indicated two temperature ranges, at which a significant
mass loss occurred. In the first range – from a room temperature to 280 °C – the
emission of heavier molecules such as xylene, benzene, and toluene occurred,
which constituted nearly 40% of the total mass loss of a binder. Slower decompo-
sition took place at the temperature range 280–540 °C. The second large mass loss,
on the TGA curve, containing 30% of the binder weight was recorded at the range
540–620 °C, and this was related to the emission of gases of a lower molecular
weight. Total combustion was finished at a temperature of 620 °C, and there was none
carbon residuals in a crucible. Dugan i Reeves [15] investigated – by means of GC/
MS methods – pyrolysis products of hardened phenol–urethane binder, carried out
at a temperature of 750 °C. The main product was benzene and its derivatives, and
the strongest signal originated from 1-methyl-2-(1-methylethyl)-benzene. Other
identified compounds present in emitted gases were 2-ethy1–4-dimethylbenzene,
1-methyl-3-(1-methylethyl)-benzene, and 1-methyl-4-(1- methylethyl)-benzene.
Phenol and its methyl derivatives were also present. From the PAHs group acri-
dine, 9-methylacridine, 2,4-dimethylbenzo(h) quinoline and 9H-xanten were
identified. From the group of volatile organic compounds, triethylamine, toluene,
o-xylene, and aniline were identified. Triethylamine was not the pyrolysis product,
but a residual of the amine catalyst applied for binder hardening, while aniline
was applied for a production of polyisocyanate [42]. In the initial phase, during a
mold pouring with liquid metal, there is an oxidizing atmosphere in a mold and
that time the higher phenol emission occurs. After some time, this atmosphere
becomes saturated with vapors of phenol and other emitted substances, which
under a rapid influence of liquid metal high temperatures are decomposing and –
in consequence – generating the reducing atmosphere. Simultaneously the com-
position of emitted gases is changing [43–48]. Gases released during pyrolysis of
biourethane binder contain CO, CO2, CH4, and various methylene esters (applied
as components of solvents) as well as several hazardous air pollutions, such as
benzene, toluene, xylene, and cresols. However, in comparison to the traditional
phenol–urethane technology, amounts of HAPs and VOC decreased by 50% and
phenol and formaldehyde emission by more than 90% [45, 46]. As indicated inves-
tigations of Wang Y. et al. [47] molding sands with biodiesel generated twice more
light gases (C1–C5), mainly alkanes and alkenes (e.g., methane, ethane, propane
etc.). Sands with traditional phenol–urethane binders produced ten times more
PAHs than sands bound by biodiesel. The authors attribute these differences to the
application of various solvents. Aromatic hydrocarbons, which under a pyrolysis
condition generated a majority of PAHs, were applied as solvents for phenol–ure-
thane binder. In respect of the HAPs emission (e.g., from BTEX group) the tradi-
tional phenol–urethane binder had comparable or even slightly smaller emission
than biodiesel. From the point of view of the environment protection, the best
advantage of the substitution of phenol urethane binder by biodiesel is a significant
decrease of PAHs emissions.
The introduction of biourethane binder allowed to eliminate – in a considerable
degree – unpleasant smell at setup of molding sand preparation and their c ompaction
in molds, but solvents can be still evolving and due to that an efficient ventilation is
needed. An occurrence of allergy to isocyanate, which can be present in the air dur-
ing sands mixing, is also possible.
The new bonding system PUROLiTe is characterized by much lower emissions
of gases hazardous for the environment (Fig. 6.9). The VOC content in the air dur-
ing the core production by shooting machine was in case of the PUROLiTe binder
Fig. 6.9 Emission of VOC and formaldehyde from molding sand with polyurethane (PUNB) and
PUROLiTe binder during making cores by means of shooting machine (0.8% of resin and 0.8% of
activator). (Reprinted by permission from Ref. [37])
Fig. 6.10 Leaching of organic compounds into the environment from spent sands (PUNB and
PUROLiTe) during their storing (0.8% of resin and 0.8% of activator); limits for individual classes
of wastes valid in Germany. (Reprinted by permission from Ref. [37])
approximately 20 times less than when the cores were produced of sands with tra-
ditional polyurethane binder. Similar situation concerns the formaldehyde emission.
Spent sands from this technology can be stored on every dumping ground, since it
was classified as waste of class “O,” while sands with phenol–formaldehyde resin
were classified to class “2” (Fig. 6.10). Castings of aluminum alloys, cast iron, and
cast steel can be made.
6.3 Resol Ester Hardened (ALPHASET)
This process (patented by British Borden Chemical at the beginning of 1980, as the
ALPHASET process) is applied at serial production of small and medium castings,
both for molds and cores [49]. It can be applied for many kinds of foundry alloys,
especially for light alloys since castings are easily knocked out. The main market
for this process constitutes steel castings, since defects related to hot-cracking are in
this process significantly reduced. The ALPHASET process is considered by some
experts as the technology of the twenty-first century [50]. This technology has
several advantages: low odor level, easy dismantling of a mold, good final surface,
small amount of veins, and minimal erosion [1].
The binder consists of highly alkaline phenol–formaldehyde resin, resol type,
soluble in water containing NaOH and/or KOH, and mixtures of organic esters sol-
uble in water (due to that, the VOC emission is low, and there is a lack of an unpleas-
ant smell). At the beginning, 1.5–2% of resin is mixed with sand, and then a mixture
of aliphatic esters is added. The reaction between the selected esters (or a mixture
of these esters) with resin containing NaOH/KOH leads to hardening/cross-linking
of a structure and to a binder solidification. In dependence on the applied ester or a
mixture of esters, the time of preliminary hardening can be regulated from 5 to
30 minutes. This technology binder does not contain nitrogen, sulfur, and phospho-
rus, due to that it can be applied for producing steel and iron castings (including
spheroidal cast iron) and aluminum alloys.4
During a mold dismantling, the molding sand with this resin indicates high plas-
ticity and a high degree of ductility, which allows for an easy removal of patterns,
even complex ones. One of the most important advantages, for producers of cast
steel castings, is the excellent hot-strength, which significantly limits the effect of
hot-cracking of cast steels.
Good points of this process are relatively low costs. Knocked out sand is highly
alkaline and can be subjected either to reclamation or stored [1, 51, 52]. The ester
hydrolysis rate, which is relatively slow, decides on the phenol–formaldehyde resin
polymerization rate. Polymerization products can significantly differ, in depen-
dence on the initial conditions of the reaction, especially the alkaline level and resin
structure.
Alkalis in phenol resins have two functions: on the one side they decrease the
resin viscosity and improve molding sand fluidity, and on the other side they cata-
lyze the hydrolysis of organic ester and hardening of phenol resins [53].
The essential advantage of this technology is a reduction of the tendency of veins
appearance in iron castings and the excellent corrosion resistance.
The hardening rate in this process is not controlled by the amount of added hard-
ener/catalyst, but by applying their various kinds (individual esters or their mixtures
of various composition) (Table 6.8). The hardening time can be changing from a
As indicated investigations of [23, 24] commercial phenol–formaldehyde resins contain nitrogen,
4
which is introduced in a form of urea in the technological process to improve resin properties.
6.3 Resol Ester Hardened (ALPHASET) 169
Table 6.8 Esters used as hardeners in the ALPHASET process and their properties
Ester hardener Reactivity Ester hardener Reactivity
Butyrolactone Fast Ethylene glycol diacetate Average
Propylene carbonate Fast Butylene glycol diacetate Slow
Glycerol triacetate Average Dibasic ester Very slow
few minutes to above 1 hour. Mechanical properties – directly after hardening – are
rather weak, but they are improving during storing [54]. The increase of the harden-
ing temperature increases the resin hardening rate. Therefore when faster hardeners
are used, the process should be carried out at lower temperatures.
Dibasic ester is a mixture of three methyl esters, derivatives of dicarboxylic
acids: dimethyl ester of succinic acid, dimethyl ester of glutaric acid and dimethyl
ester of adipic acid. It is applied as component of solvents and plasticizers and as a
solvent of several resins.
The hardening technology of alkaline phenol resin by esters was introduced into
the foundry practice, as the one which will improve work conditions at the molding
sands preparation as well as at the mold pouring with liquid metals [3]. This tech-
nology can be applied on automatic forming lines.
In case of castings of high-manganese cast steel using olivine sand as a matrix is
advantageous, since manganese oxide does not react with silica (which is bound
into forsterite Mg2SiO4 and fayalite Fe2SiO4) and due to that burn-on does not occur.
It can be seen from the data placed in Table 6.9, the tensile strength of molding
sands obtained in the ALPHASET technology increases with the hardener increase
from 10% to 30% and then decreases.
In order to increase strength and to improve a moisture resistance of sand an
addition of a small amount of silane into resin (app. 0.1–0.3% of the resin amount)
is necessary. This addition acts as a factor joining inorganic surface of sand grains
with the organic binder.
The Hardening Mechanism of the Binder Based on Alkaline Phenol–
Formaldehyde Resol Type Resin
The hardening mechanism of the phenol–formaldehyde resin by means of esters is
quite complex and not fully explained yet. It especially concerns the ester function
as a hardener, while simultaneously catalyzing the hardening process.5 Investigations
of this process performed in the last years with applications of modern analytical
methods, DSC (differential scanning calorimetry), MS (mass spectrometry), GC
(gas chromatography), and FTIR (Fourier transform infrared spectroscopy), pro-
vided several information helpful in explaining this mechanism [55–61]. Renhe
H. et al. [61] – using measuring techniques (IR and TG) – investigated the influence
of the pH, hardener type, and temperature on the hardening reaction of phenol–
formaldehyde resin by means of esters. They found that the organic ester is only
5
The mixture of organic esters is often referred to as the name of the catalyst/hardener because on
the one hand it accelerates the cross-linking and hardening reaction of the resin but also takes part
in this reaction, partially consuming [76].
Table 6.9 Influence of the amount of ester hardener of a medium hardening rate (glycerol
triacetate +1,4 butyrolactone) on the tensile strength of molding sand from the ALPHASET
technology
Amount of hardener Tensile strength of molding sand, MPa
(% of the resin) After 2 h After 12 h After 24 h
10 0.23 0.26 0.23
20 0.43 0.49 0.58
30 0.47 0.66 0.83
40 0.27 0.32 0.61
O O
R1 R1 + R2OH
R2 + OH– O
O
R1COOR2 + OH– R1COO– + R2OH
Fig. 6.11 Hydrolysis reaction of ester in a basic environment
partially hydrolyzed and the resin can be hardened in the reaction with hydrolyzed
ester as well as in the reaction with the excessive not hydrolyzed organic ester.
After analyzing the obtained results, these authors proposed the hardening mech-
anism of alkaline phenol–formaldehyde resin by organic esters. According to them,
the hardening process starts as the hydrolysis reaction of organic ester, in a highly
basic environment, and as the result acid and alcohol is formed (Fig. 6.11).
The hydrolysis reaction of organic ester is a slow one, and it controls the resin
hardening process in its initial phase [61]. Large amounts of heat are emitted during
this hydrolysis. Acid formed as the hydrolysis result neutralizes alkalies present in
the resin and lowers pH of the system, which – in consequence – decreases the alka-
line resin solubility in water. That time appears a gel. When pH of the system falls
to 10.8–10.88, a fast hardening reaction occurs between excessive organic ester and
phenol resin. One of the elements of this reaction contains the exchange of the
hydroxyl group from the hydroxymethyl resin (or with hydroxyl group from phe-
nol) and the ester group, which causes the formation of the intermediate resol ester
(Fig. 6.12).
This intermediate resol ester undergoes decomposition into quinone methide
(Fig. 6.13) and a preliminary cross linking of the resin occurs.
The subsequent stage contains formation of bridges either methylene (−CH2−)
or dimethylether (−CH2−O−CH2−) bridges in between aromatic chains.
In general, the reaction of the phenol–formaldehyde resin with organic esters can
be written as follows (Fig. 6.14):
Alkaline phenol-formaldehyde resin + ester → intermediate transient product →
decomposition with forming: alkaline salts of polymerized phenol resin +
alcohol
C O
ONa R1 C OCH3 O
CH2ONa CH2ONa NaOCH2 CH2 - O - CR + CH3ONa
ester
CH2ONa CH2ONa
alkaline phenol formaldehyde resin intermediate resol ester sodium alcoholate
Fig. 6.12 Reaction of the ester (hardener/catalyst) with −CH2O group from the resin
Fig. 6.13 Quinone methide is an active intermediate substance, facilitating hardening of alkaline
phenol resin
Mechanical Reclamation: Influence of Alkaline Metals

Molding sands from the ALPHASET technology (like other sands of a basic char-
acter) are rather difficult for the reclamation by conventional methods of dry grind-
ing, since on surfaces of matrix grains basic salts are precipitating (Table 6.10).
These salts, in case of quartz matrix, can form silicates worsening binding proper-
ties of the reclaim [24, 27, 62–64].
Alkaline salts can be changing the sand surface chemical composition and
remain in sands. This can be the reason of a weaker bonding in molding sands where
a reclaim was used. This also causes that the reclaim appears “dry” by absorbing
water from resin. Generally, at the mechanical reclamation, sodium salts are less
unfavorable than potassium salts. Therefore using resins with additions of sodium
hydroxide is preferred, when the mechanical reclamation is applied. Water additions
of 0.2–0.3% in relation to a molding sand amount improve also bonding properties
of the reclaim [65–67].
Bonding of Molding Sands Containing a Reclaim
A reclaim, apart from the fact that it contains certain amounts of spent organic mate-
rials, contains also alkaline salts remained after the reclamation process. A kind of
these salts depends on the ester applied for a polymerization, since some esters have
Na/KOCH2
Na/K
O
O
H2C
K/NaOH2C CH2ONa/K + H2C O CH3
R O
ester H2C
Na/KOCH2
CH2ONa/K
Alcohol CH2ONaX
RCOOK/Na
salt
Fig. 6.14 General scheme of the reaction of phenol–formaldehyde resin with ester
Table 6.10 Obtained levels of molding silica sand reclamation, based for selected technologies
[64]
Average level of Maximum level of
Process reclamation (%) reclamation (%)
Alkaline phenolics ester hardened 75 85
(ALPHASET)
Furan sulfonic acid catalyzed 85 95
Phenolic–urethane no-bake 85 90
a higher influence on the bonding character. When the reclamation process was not
applied, these alkaline salts do not need to be taken into account.
Alkaline salts remained in a reclaim can occur in two forms: oxidized salts,
insoluble in resins, and unoxidized salts, which are well soluble in resins applied for
binding molding sands containing a reclaim. Fractions of soluble and insoluble salts
depend on a temperature, to which they are exposed during pouring and cooling. At
a small ratio of a molding sand to metal (high overheating of a molding sand), the
amount of the remained soluble salts is smaller. A fraction of soluble salts contained
in a molding sand destined for rebinding will be the function of their amounts
present in a molding sand, which was subjected to a reclamation, and of its mixing
degree with fresh sand in a mixer.
Influence of Alkaline Soluble Salts on the Bonding Character in a Molding
Sand with a Reclaim Addition in the ALPHASET Technology
The kind of alkaline salts present in a reclaim obtained by the mechanical reclama-
tion method is the function of the kind of ester (or esters), used for the initial polym-
erization of resin added to a molding sand before the reclamation. Certain amounts
of alkaline salts can be in non-hydrated form or in only partially hydrated form.
Such salts are easily solvable in water. These salts will be present on sand grains
surfaces and will be easily available for reacting with new resin and ester added to
a molding sand with a reclaim. Resins applied in the ALPHASET technology are
water soluble and therefore – it can be assumed – that all soluble alkaline salts will
be easily captured by the introduced new resin and thus the number of accessible
metal ions will increase. This increase of the metal ions content accelerates the
neutralizing process, described previously, and shortens the molding sand work
time. This shortening of the sand work time is substantially different than in resin
systems bound with a participation of a catalyst and must be taken into account,
when a reclaim is used.
A reaction dynamics in the ALPHASET process is determined by the kind of
ester applied for a polymerization. In order to obtain very short times of a prelimi-
nary hardening (strip time), the application of highly reactive esters (which are char-
acterized by a very short work time) is necessary. When soluble alkaline salts are
present in a reclaim because very fast esters were applied, the work time would be
reduced. For instance, a molding sand on fresh sand with very fast ester can have the
real work time slightly above 1 minute at 20 °C. When the same ester is applied for
a reclaim, the real work time will probably decrease to not more than 50% in rela-
tion to 1 minute of a molding sand on fresh sand.
Thermal Reclamation: Influence of Alkaline Metals
The influence of alkaline metals, in case of the thermal reclamation, is even more
disadvantageous, than in the mechanical reclamation [68]. Salts of alkaline metals
will react with high-silica sand forming quartz glass. These sintered silicates can
damage the reclaimer. In addition, potassium or sodium salts can be building in into
the obtained reclaim, weakening the strength of a molding sand with bentonite. To
prevent this effect, the special additions are introduced into the knocked out mold-
ing sand just before its introducing into the thermal reclaimer. These additions intro-
duced in amounts of 0.6–1.0% minimize the sintering process in a wide temperature
range. They form complex compounds with alkaline metals and remove them in a
form of dusts.
In a similar fashion as in case of the mechanical reclamation, a water addition
will advantageously influence the strength of a molding sand prepared on the
reclaim matrix. It is possible to apply 60–80% of a reclaim obtained by means of the
mechanical method while nearly 100% of a reclaim obtained by the thermal method
(provided that special addition was introduced into a molding sand before its ther-
mal reclamation). In order to achieve the maximum level of utilizing a spent mold-
ing sand (based on olivine sand) from the ALPHASET technology, the three-step
reclamation system is applied. This system contains conventional system of
preliminary reclamation by rubbing, secondary reclamation system by rubbing, and
the thermal reclamation. Properties of the reclaim as well as of molding (Table 6.11).
Table 6.11 Comparison of physical properties of fresh olivine sand, its reclaim after mechanical
and thermal reclamation
Matrix Loss on ignition (%) Dust (%)
Fresh olivine sand 0.13 0.76
Reclaim after the second stage mechanical 0.71 0.22
reclamation
Reclaim from thermal reclamation 0.05 0
Factors Deciding on the Ester Selection: Work Conditions

When the decision, concerning the selection of individual components for the given
resin, is to be taken, knowledge of conditions under which the technology will be
operating is necessary as well as the requirements of the user must be known. When
sand temperature will be below 15 °C, applying of faster hardeners can be neces-
sary, to maintain the required time of a preliminary hardening. When large castings
are produced, slow esters are used as hardeners.
Water Addition for Equalizing the ALPHASET Reaction Dynamics
When the addition of a reclaim from the ALPHASET technology is applied, the
reactivity increase caused by dissolved remains of alkaline salts originated from
fresh resin can be counteracted by a water addition into a mixer just before the resin
introduction.
This additional water maintains a polymer in a solution for a longer time during
its hardening and thus makes possible a more complete polymerization of resin.
Simultaneously the ester neutralization process slows down. The required amount
of water depends on the burning degree. Too high amount can be disadvantageous.
When water is added to a fresh molding sand, it can potentially lead to defects in
castings.
Ester plays quite different function in the ALPHASET process than catalysts in
the hardening processes of furan or urethane resin, despite that it is often also called
the catalyst. The hardening mechanism of alkaline phenol–formaldehyde resin is
rather the highly reactive chemical process and not a catalytic process. Catalysts are
applied for accelerations of a polymerization in hardening processes of furan resins.
The polymerization rate is controlled by the amount of added catalyst. This catalyst
is not changing in the polymerization process and, even after a total hardening,
remains in its initial form. None side products are formed.
Changes of the work time and strip time of a molding sand in the ALPHASET
technology are controlled by changes of the applied ester. Ester is added – in prac-
tice – in the constant ratio in relation to resin. An increase of the ester addition above
the established level does not influence the molding sand parameters. However,
when the smaller amount of ester – than it was established – will be added, a mold-
ing sand will have lower strength parameters, since there will not be enough of ester
for the total cold polymerization. It is possible to apply slower or faster esters from
the available range of products. In the ALPHASET technology one is dealing with
the chemical processes of resin hardening, which occurs in two stages: the prelimi-
nary polymerization at a low temperature and the total polymerization at a high
temperature.
OH
CH2 OH
CH2
CH2 O
OH CH2OH
CH2O CH2
CH2 CH2OH
O OH
CH2 CH2 HO
CH2
CH2 CH2
O
OH +ROH, RCOO–M+, H2O
OH CH2 CH2
CH2 CH2 CH2 CH2-OR

O
CH2
Fig. 6.15 Structure of polymerized alkaline phenol–formaldehyde resin hardened by esters
Since a polymerization at an ambient temperature is only a partial polymeriza-

tion, the binder based on alkaline phenol resin will never reach at a room temperature
the same cold-strength as furan or urethane cold-hardened sands. The structure of the
polymerized phenol–formaldehyde resin hardened by esters is presented in Fig. 6.15.
Influence on the Environment
Molding sands with alkaline phenol–formaldehyde resol type resin (hardened by
esters) are characterized by a significantly lower negative influence on the environ-
ment and work conditions than sands with furan resin (Table 6.12).
Additional parameters related to assessing the harmfulness of molding sands
technologies with furan resin and with alkaline phenol resin are presented in
Tables 6.13.
During pouring of molds, made in the ALPHASET technology, with molten met-
als the emission of substances from the BTEX group (Table 6.14) and substances
from PAHs group (Table 6.15) occurs.
The most visible influence on amounts and compositions of gases emitted from
molds, after their pouring with liquid metal, has the temperature of this metal. The
volume of gases evolving from a molding sand after pouring with aluminum alloy
(app. 700 °C) was several times smaller than after pouring with cast iron (1350 °C).
The benzene content in gases emitted from the mold poured with aluminum alloy
was more than ten times smaller than from the mold poured with cast iron. Amounts
of remaining substances from the BTEX group are very similar to each other.
Table 6.12 Emission of gases from molding sand with alkaline resol resin (ALPHASET) and
with furan resin
Emission during making Emission during pouring with
Technology Hardener mold molten metal
ALPHASET Mixture of Formaldehyde Aromatic hydrocarbons
esters Phenol Phenol
Esters Formaldehyde
Mono and di carbon oxide
Furan resin Sulfonic acid Formaldehyde Mono and di carbon oxide
Phenol Phenol
Furfuryl alcohol Formaldehyde
Hydrogen sulfide Aromatic hydrocarbons
Sulfur dioxide Sulfur dioxide
Acids mist Ammonia
Aniline
Table 6.13 Characteristic of the molding sand before pouring with molten metal
Parameter ALPHASET Furan resin
Loss on ignition, % 1.4 3.1
PAHs, mg/kg <0.12 <0.12
Organic compounds as total organic <0.12 2.2
carbon (TOC), mg/kg
Table 6.14 Emission of compounds from the BTEX group released during pouring of the cores
from ALPHASET technology with cast iron and aluminum alloy AK 11
Gas emission, [mg/g of
Molten metal and kind of The volume of released gases, resin]
matrix (dm3/g of resin) B T E X
Cast iron (quartz sand) 1.041 18.07 1.09 0.01 0.13
Cast iron (olivine sand) 1.777 33.98 1.32 0.01 0.15
Aluminum alloy AK 11 0.260 1,40 0.87 0.169 0.18
(quartz sand)
B benzene, T toluene, E ethylbenzene, X xylenes
Molding sand composition: phenol–formaldehyde alkaline resol resin, 1.5%;

ester hardener, 0.3%; high-silica sand. The largest fraction in evolving PAHs con-
stituted naphthalene (nearly 20%). Significant amounts of pirene and fluoranthene
also occur. Systematic and extensive research on the thermal destruction ester cured
phenol–formaldehyde resin, using modern research methods Py/GC/MS and TG/
FTIR, lead the Holtzer M. and Kmita A. team [23, 24, 70, 71] using different
atmospheres (inert, oxidizing, and reducing) and different temperatures of destruc-
tion (in the range of 500–1100 °C). These research allowed to determine the type of
gases emitted during the “flash” pyrolysis by the Py/GC/MS method and “slow”
pyrolysis by the TG/FTIR method. Exemplary chromatogram Py/GC/MS obtained
Table 6.15 Emission of compounds from the PAH group (sample of molding sand pouring by
cast iron, matrix – quartz sand) (sampling according to the methodology described in [69])
Concentration Concentration
Compounds (μg/1 g of resin) Compounds (μg/1 g of resin)
Naphthalene 200.25 Chrysene 21.71
Acenaphthylene 50.84 Benzo (b) fluoranthene 76.95
Acenaphthene 0.45 Benzo (k) fluoranthene 39.36
Fluorene 9.45 Benzo (a) pyrene 34.04
Phenanthrene 94.53 Indeno (1,2,3-cd) pyrene 38.93
Anthracene 26.81 Dibenzo (ah) anthracene 7.59
Fluoranthene 107.78 Benzo (ghi) perylene 31.21
Pyrene 136.93 Benzo(a)anthracene 46.06
Total 922.91 ± 184.58
as a result of the “flash” pyrolysis of the commercial resin used in the ALPHASET
technology is shown in Fig. 6.16, and in Table 6.16 indicate the identified gases
released during pyrolysis at 500 and 700 °C.
Investigations of spent molding sands originated from the ALPHASET technol-
ogy indicated the PAHs presence. Moreover, the concentration of these compounds
was dependent on the kind of the cast alloy, which really means that was dependent
on the temperature.
Molds were poured by cast iron, cast steel, copper alloy, and aluminum alloy.
The largest amount of PAHs contained the molding sand, in which iron castings
were made – 240 mg/kg of sand. In the remaining molding sands, PAHs amounts
were below 2 mg/kg of sand and equaled: for copper alloys castings, 1.99 mg/kg of
sand; for cast steel castings, 1.47 mg/kg; and for aluminum alloy castings, 1.23 mg/
kg of sand. For all alloys the main substance from the PAHs group is naphthalene,
which constitutes 30% (in case of sand originated from aluminum alloys castings
naphthalene equals more than 50%). Concentration of the remaining organic sub-
stances (benzyl aldehyde, benzyl alcohol, ketones, esters, phenols, ethers, fatty
acids esters, glycol derivatives) in spent sands equaled – in total – from 0.8 to
5.6 mg/kg of sand.
Concentrations of metals, which were undergoing leaching (As, Ba, Cd, Cr, Pb,
Se, Ag, Cu, Zn), in filtrates obtained from spent sands originated from making cast-
ings were cast steel castings, 0.388 mg/dm3; iron castings, 0.327 mg/dm3; aluminum
alloy castings, 0.658 mg/dm3; and copper alloy castings, 189.94 mg/dm3 (such high
concentration was the result of the fact that in the copper alloy casting were present
Pb and Zn, being the alloy components and easily leaching) [51, 73].
Fig. 6.16 Py/GC/MS chromatogram obtained as a result of the “flash” pyrolysis of the commer-
cial resin used in the ALPHASET technology at 700 °C [72]
6.4 Alkyd Oil, No-Bake
Binders applied in this technology consists of three components: component A -

alyd resin, modified by drying oil, component B - liquid amine or metallic catalyst,
called alkyd activator and component C - polyisocyanate [48]. Binding of molding
sand occurs in two stages: in the first stage polyisocyanate (isocyanate groups) react
with alkyd resin (with its hydroxyl groups) and urethane binder is formed. In the
second stage, the oil is oxidized and polymerized. In result, the polyurethane binder
is formed, which constitutes the proper agent bonding sand matrix grains [3]. Since
polyurethane binder is characterized by a long hardening time, this process can be
accelerated by means of a catalyst and – in addition – by heating a molding sand to
a temperature of 150 °C.
This technology is applied for steel castings production. A matrix can be of high-
silica sand or chromite sand. Its advantage is very good quality of the casting sur-
face, knocking out ability and relatively low sensitivity to a temperature (sand
temperature can be even reaching 50 °C). Molding sands are characterized by a high
strength, good moisture resistance, satisfactory erosion resistance, and moderate
gas emission rates [74].
6.4 Alkyd Oil, No-Bake 179
Table 6.16 List of the identified gases released during pyrolysis, at 500 and 700 °C, from
commercial resin used in the APLHASET technology [72]
Pyrolysis temperature
Retention Molecular (°C), fraction (%)
No time (min) CAS No Compounds weight 500 700
2. 2.10 124–38–9 Carbon dioxide (CO2) 44 47.68 41.28
8. 7.77 108–88–3 Toluene (C7H8) 92 0.85
9. 11.65 108–38–3 1,3-Dimethyl benzene 106 4.30
(C8H10)
11. 15.23 526–73–8 1,2,3-Trimethylbenzene 120 9.06
(C9H12)
13. 17.62 108–95–2a Phenol (C6H6O) 94 7.71 6.02
15. 20.03 95–48–7 o-Cresol (C7H8O) 108 7.33 16.25
16. 20.65 106–44–5 p-Cresol (C7H8O) 108 2.04
17. 21.68 95–87–4a 2,5-Dimethylphenol 122 9.22 7.48
(C8H10O)
18. 22.84 105–67–9 2,4-Dimethylphenol 122 12.39 8.26
(C8H10O)
21. 24.43 2416–94–6 2,3,6-Trimethylphenol 136 4.46
(C9H12O)
Compounds with carcinogenic and mutagenic effects
a
Alkyd molding sands are convenient in everyday applications. They are nearly
odorless. The critical parameters at alkyd resin applying as a binder of molding
sands are:
• High viscosity of a binder and isocyanate, which makes difficult the accurate
dosing and mixing of components
• Affinity of drying oil (which is a binder component) to oxygen from the air,
which causes formation of oxidized layer (“scum”) on the binder surface in a
storage tank
• Affinity of isocyanate to the air humidity also giving certain binding product on
the liquid surface in a storage tank
In order to avoid these problems special operations should be performed. Both
liquid components (resin and catalyst/hardener) must be kept in heated storage
tanks, with stabilized temperature. The neutral gas – the best, argon – should be
introduced to both tanks, since it will protect liquids against a negative air influence.
Alkyd resin-based binders, which found applications in foundry practice, are
hardened by isocyanates. Alkyd resins are applied for producing molds and cores.
High-silica and chromite sands can be used as matrices. These sands are especially
suitable for producing steel castings, where they can constitute the competence for
molding sands with furan resins. Generally molding sands containing 1.0–1.3% of
resin and a hardener being 25% of the resin amount. This process is called the
Ashland alkyd process.
Table 6.17 Results of the analysis of gases from the BTEX group released from molding sand
with alkyd binder (alkyd resin + polyisocyanate) (Commercial resin: A, B, and C come from
different manufacturers) during semi-technical scale tests
The volume of gases dm3/kg of molding Concentration, mg/kg of molding sand
Sample sand Benzene Toluene Ethylbenzene Xylenes
A 17.61 448.548 19.712 0.405 23.417
B 15.799 442,697 12.462 1,37 6.410
C 20,367 605,91 29,45 2,75 13,69
Table 6.18 Results of the PAHs analysis in gases emitted from the molding sand (calculated on 1
kg of molding sand) with resin A after pouring by cast iron at the temperature 1350 °C
Concentration Concentration
Compounds (μg/kg) Compounds (μg/kg)
Naphthalene 2237.6 Chrysene 15.01
Acenaphthylene 30.01 Benzo (b) fluoranthene <2.34
Acenaphthene 15.39 Benzo (k) fluoranthene <2.03
Fluorene 111.72 Benzo (a) pyrene 5.93
Phenanthrene 466.06 Indeno (1,2,3-cd) pyrene <1.66
Anthracene 123.86 Dibenzo (ah) anthracene <1.62
Fluoranthene 143.01 Benzo (ghi) perylene <1.68
Pyrene 67.04 Benzo(a)anthracene 23.87
Total 3250 ± 651
The highest amount of naphthalene, substance containing two aromatic rings, was formed

The results of semi-technical tests of emissivity of gases, from the BTEX group,
generated when the molding sand with alkyd resin was poured with liquid cast iron
of a temperature of 1350 °C, are presented in Table 6.17 [75]. The results of the
analysis of compounds from the PAH group in gases emitted from the molding sand
with resin A after pouring with molten cast iron are present in Table 6.18 [32].
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Chapter 7
Gas-Hardened Processes (Cold-Box)
Molding sand hardening in these processes occurs due to the influence of a catalyst
or hardener in a gaseous form, at a room temperature. The hardening rate can be
very fast, and therefore a highly efficient production is possible. These technologies
are suitable for making molds and cores of limited dimensions, in medium or mass
series. Chemical bases of several processes hardened by gases are similar to cold-
hardening processes. On account of a gaseous form of a catalyst, the necessity of
building installations for catching and neutralizing these gases sometimes can occur.
Amines, CO2, SO2, and methyl formate are applied as gaseous catalysts/hardeners.
This group of processes has several advantages, among others:
• There is no need of heating a core box to a high temperature, and due to that the
core box lifetime is longer and energy is saved
• High-quality cores are achieved
• High efficiency
Since within this group of technologies not only neutral gases but also harmful
and toxic gases are applied, these processes require a special care. Therefore it is
necessary to develop a new process (from this group) in which only gases harmless
for people and the environment will be used.
7.1 SO2 Hardened Furan Resins (HARDOX)
This process is presently utilized to a small degree only, although it is convenient for
a wide range of castings of various alloys, made in small and medium molds and
cores (this process was implemented in foundry plants in 1975). A hardener con-
taining sulfur can be causing changes of the surface layer microstructure of castings
made of spheroidal cast iron. The main advantages of these molding sands are pos-
sibility of achieving a long lifetime, good mechanical properties, and knocking-out

186 7 Gas-Hardened Processes (Cold-Box)
ability as well as prevention against cracks. Nevertheless the implementation of this

technology is limited, due to the application of dangerous SO2 as a hardener.
Furan resins containing up to 80% of free furfuryl alcohol and phenol resins are
used in this process. Both resins polymerize in the acidic environment. Resins are
mixed with sand and oxidizing agent (which can be organic peroxide or hydrogen
peroxide) and then blown into the core box and blown through by SO2. Oxidizer
changes SO2 into SO3, which reacts with water contained in a molding sand forming
sulfuric acid (VI), which is causing a fast polymerization of resin (Eq. 7.1).
catalyst
SO2 + 1 / 2O2 → SO3
heat (7.1)
SO3 + H 2 O → H 2 SO 4

After blowing through by sulfur dioxide the core box or mold is subjected to the
run-purge, aimed at removal of gas which did not react. Sulfur dioxide is absorbed
in NaOH solution, where it is neutralized (Eq. 7.2).
SO2 → SO3 + 2 NaOH = Na 2 SO 4 + H 2 O (7.2)

Sands of a low ADV and of a temperature of app. 25 °C should be used. Molding
sand: composition, 1.2–1.4% of resin and 25–60% (in relation to resin) of a hardener
(e.g., peroxide of methylene–ethylene ketone). Resin does not contain nitrogen. At
first, resin is added to sand, then oxidizer and organic additions. Gas consumption
equals app. 2 ml of liquid SO2/1 kg of sand. After 6 hours cores achieve tensile
strength of 250 kPa. Since SO2 has strongly corrosive properties, there is a danger of
damaging its transferring installations. This technology is applied mainly in non-
ferrous metals castings, where a high dimensional accuracy and easy removal of
burned molding sand is required. Sulfur dioxide is a gas of acrid, suffocating odor,
strongly irritating breathing lines of those who have the odor perception threshold
below 0.5 ppm. Sulfur dioxide is poisonous for animals and harmful for plants. It has
antibacterial and anti-mildew properties. It dissolves in water and acetone. Therefore
monitoring and controlling of SO2 concentration at the workplace is necessary. When
high temperatures influence molding sands with this binder, SO2 is emitted [1–4].
7.2 Amine Hardened Phenolic–Urethane Cold-Box (PUCB)
The cold-box process utilizing polyurethane binders was implemented in foundry

plants in 1968. This process is known as PUCB – phenolic–urethane cold-box or
phenolic Ashland process [4]. Its application, both in the USA and EU, is growing.
This process is mainly applied for production of cores weighing 100 kg and of
larger and smaller molds. Its advantages are very smooth surface and high
dimensional accuracy. Cores’ knocking out ability is excellent, and spent molding
sands can be easily reclaimed. This is the most often applied process of the core
production.
7.2 Amine Hardened Phenolic–Urethane Cold-Box (PUCB) 187
Binder in the this cold-box technology contains two components: component 1

is a solution of phenol–formaldehyde resin, while component 2 is a solution of
polyisocyanate. Resin and polyisocyanate are mixed with sand and then shot into
the core box. This core box is blown through by gasified tertiary amine (component
3), which catalyzes reaction between component 1 and component 2. Both binder
components contain special additions, applied in order to optimize special binder
properties (e.g., resistance to moisture content). Applied solvents have to provide
the appropriate fluidity of individual components allowing their mixing with sand.
In addition, solvents control the main properties of molding sands: lifetime, resis-
tance to moisture content, and possibility of applying hydrous protective coatings.
In consideration of polarity differences of polyisocyanate and phenol resin the pos-
sibility of finding – such solvent which would be compatible with these both com-
ponents – is very limited. This compatibility is necessary for the reaction going to
its end and for fully hardened binder. Polar solvents of the dibasic esters type (it is
a mixture of three esters of organic dicarboxylic acids) are suitable for phenol resin,
but not very good for isocyanate. Exactly the other way round is the situation in case
of non-polar solvents. More and more often special additions, which increase the
molding sand resistance to moisture content, prolong lifetime, and make easier
removing cores from core boxes, are used in this technology [5, 6]. Organic acid
chlorides are used as inhibitors of the reaction of urethane forming in the mixture of
sand, resin, and isocyanate. Inhibitors are introduced into isocyanate in amounts
from 0.01% to <1.0% versus the isocyanate amount. Chlorides of organic acids
applied as inhibitors are very sensitive to a moisture content and can hydrolyze
forming hydrochloric acid. Isocyanate is also sensitive to a moisture content and can
be forming solid polyurethane, which will block pumps, feeders, etc.
Component 1 is added into the mixer containing sand as the first one, and then
component 2 is introduced. The mixture should not be mixed too long, because it
can become too hot, and solvents might evaporate. The service life of molding sands
equals 1–2 hours.
Tertiary amines, the most often in a mixture form, are used: triethylamine (TEA),
dimethylethylamine (DMEA), dimethylisopropylamine (DMIPA), or trimethyl-
amine (TMA) (Fig. 7.1). These amines are alkaline liquids of corrosive properties;
they are flammable and should be stored and applied with taking great precautions.
They are of unpleasant odors. Amine in a gaseous state is introduced into the core
in amounts of 0.2–1 ml/kg of core in a stream of the dry compressed air under the
C3H CH3
CH3 CH3 CH3
N
CH2 N CH3 N
CH3 CH2 N CH2 CH3 C3H CH3 H3C H3C CH3
triethylamine dimethylisopropylamine dimethylethylamine trimethylamine

TEA DMIPA DMEA TMA
Fig. 7.1 Structural formulae of amines applied in the cold-box process

pressure of 200–300 kPa. Amine, after hardening, remains partially in the core
(mold), out of which it is removed by the air stream. The carrier gas should be
heated to a temperature of 30–40 °C, to assure the amine evaporation.
The binder fraction is within the range 1.0–2.0% versus the sand weight, at the
ratio of resin: isocyanate being 1:1. Usually it is app. 1.5% of a binder, and in case
of castings made of aluminum or magnesium alloys, a molding sand contains less
than 1% of a binder, which significantly improves its knocking out ability. Directly
after hardening, cores achieve the tensile strength of 2000 kPa. The storage of cores,
under conditions of a high moisture content, causes their strength decrease. The
application of hydrous protective coatings also participates in strength decreasing.
The majority of amines applied in this technology, at a room temperature, is in a
liquid state, and before their introduction to the core box they have to be transferred
into a gaseous state. The exception constitutes trimethylamine (TMA), which boil-
ing point is 3 °C. Due to that, complicated installations for gassing liquid amines
can be avoided, the amine consumption is smaller (by 78%), and time of blowing
through is shortened (by 54%) as compared with varieties of cold-box process using
amines, which are liquid at a room temperature. To this effect, the efficiency of the
core production with the application of TMA increases by 30%. The main reaction
rate and thereby the core hardening rate as well as properties of the final product are
highly dependent on the formation rate of the amine intermediate compound; it
means on the catalyst (amine) properties. Increases of the efficiency of the core-
making machine, and decreases of a material consumption provide significant sav-
ings for foundry plants and improve the environment state. In case of storing the
cores hardened by TMA, an emission of amines is significantly reduced. In depen-
dence on requirements concerning the final product, the appropriate catalyst is
applied. This reaction would be also occurring without any catalyst, but it would be
much longer.
Both resin (component 1) and polyisocyanate (component 2) (Fig. 7.2) are dis-
solved in appropriate solvents, in order to decrease their viscosity and to improve
their placement on grains surfaces.
The isocyanate group -N=C=O is reactive, since it contains two cumulated dou-
ble bonds. Easily volatile isocyanates are very toxic. During the binder hardening
the emission of unreacted isocyanate also occurs. The emission amount depends on
the reactivity of individual cyanate. MDI has smaller vapor pressure and therefore
is less toxic than TDI (Fig. 7.3).
The base of the Ashland’s phenol process, i.e., the classic cold-box process, is
polyurethane reaction (Fig. 7.4) consisting of the reaction between hydroxyl groups
of phenol origin (component 1) and isocyanate NCO- groups (component 2). Amine
catalyzes the reaction between phenol–formaldehyde resin and polyisocyanate, by
forming intermediate complex.
Then hardened polyurethane binder is formed (Fig. 7.5).
The rate of the above reaction, and thus the core hardening rate, depends on the
intermediate complex formation rate, which – in turn – depends on the amine mol-
ecule size.
Fig. 7.2 Components of binder for cold-box technology
Fig. 7.3 Toluene diisocyanates used in cold-box technology
Amines, applied as catalysts, have boiling points significantly below 100 °C, and
this temperature is proportional to the amine molecular mass (Table 7.1). The larger
molecular mass of amine, the higher its boiling point, and the more difficult its gas-
sing. In effect, the amine tendency to condensate in the supplying system and even
in the core is growing. The applied tertiary amines differ in their reactivity and
price. TEA amine is the less reactive and the cheapest, while amines DMEA and
TMA are more reactive, have lower boiling points, and simultaneously are much
HO HO HO
HOCH2 CH2 O CH2 CH2 CH2OH + O C N R N C O + CH3 N CH3
CH3
m n
NH C O R O C NH R NH C O R
O O O
n
Fig. 7.4 Reaction of the cold-box process with using polyisocyanate
Fig. 7.5 Hardened polyurethane binder
Table 7.1 Properties of tertiary amines [2, 4, 7, 8]

Parameter TEA DMIPA DMPA DMEA TMA
Name Triethylamine Dimethyliso- Dimethyl- Dimethyl- Trimethyl-
propylamine propylamine ethylamine amine
CAS no 121-44-8 996-35-0 926-63-6 598-56-1 75-50-3
Formula (C2H5)3N (CH3)2C3H7N (CH3)2C3H7N (CH3)2C2H5N (CH3)3N
Molecular 101.19 87.16 87.16 73.14 59.11
weight
(g/mol)
Boiling 89–90 64–67 36–38 3
temperature
(°C)
Density (g/cm3) 0.728 0.72 0.701 0.676 0.67
Basicity (pKa*) 10.65 10.30 9.99 9.8
Flash point −15 −27 −18 −46 −65
(°C)
Purity (%) >99.0 >99.0 >99.0 >99.0
Content of <0.5 <0.5 <0.5 <0.5
water (%)
Solubility (g/ 133 Unlimited Unlimited Unlimited
dm3) (20 °C) In H2O In H2O In H2O
Vapor pressure 69 170 580 2200
(mbar) (20 °C)
Self-ignition 215 190 190 190
temperature
(°C)
Reactivity Standard Faster The fastest The fastest
more expensive. DMIPA amine has properties intermediate of amines: TEA and
DMEA. Efficiency of these amines is presented in Table 7.1 [9]. The amines activity
increases with increasing alkalinity. On account of an unpleasant odor and harmful-
ness of amines, the workplace for making cores in this technology must be hermetic
and must be equipped with an efficient ventilating hood. An excess of amine is
gathered in washers with sulfuric or phosphorous acid. Amine sulfate or phosphate,
formed there, are subjected to processing in order to reclaim amine, which can be
again introduced to the system [10].
Traditionally, in the core hardening process, only one kind of amine is applied in
gassing. The phenol–urethane resin hardening technique in two stages is described
in paper [9]. At first a core is blown through by less reactive amine (cheaper) and
then by more reactive amine (more expensive). A partial substitution of more expen-
sive amine by cheaper one makes the core production process by means of the cold-
box technique more profitable [7, 8].
In addition, the above technique increases the process efficiency since it shortens
the time of producing individual cores. A decrease of amine usage favorably influ-
ences work conditions in foundries.
The classic cold-box process, apart undeniable very positive features, has essen-
tial drawbacks. Its negative feature constitutes a high sensitivity to moisture content
of isocyanate.
Also cores and molds produced by means of this technology have a high sensitiv-
ity to moisture content, which decreases their strength. This is a result of a weak
cross-linking of polyurethane molecules, caused by a high hardness rate [4, 11].
Even 0.5% of a moisture content decreases the molding sand strength by 30% and
shortens the allowable time of core storage. The source of moisture can be sand, the
air applied for core blowing through, the air applied for shooting molding sands, as
well as the surrounding atmosphere [12].
On account of that, the variety of this process, called “Process Cold-box Plus,”
was developed. In this process a core box is heated to a temperature 40–80 °C by
means of circulating hot water vapor. The core box heat influences a few millimeters
inside a core, not causing hardening of a molding sand introduced into the core box.
A molding sand hardening occurs only after blowing by amine. Cores of better
strength properties are obtained in this technology; however interruptions between
producing successive cores are longer.
High-silica, well-dried sand (moisture content up to 0.1%) of as low as possible
content of clay (up to 0.2%), of globular or oval grains, is usually applied as a
matrix. Other sands can also be used, but olivine sand should not be applied, since
it is characterized by a high basicity, which causes fast bonding and significantly
decreases the molding sand working time. The optimal sand temperature is 25 °C.
As far as in the traditional process, the applied amines are – at a room tempera-
ture – liquids and before the introduction into the core box must be changed into a
gaseous state, whereas in the ESHAMINE Plus process (developed by the FOSECO
Company), TMA (trimethylamine) is applied, which at a room temperature is a gas
(boiling point of this amine equals 3 °C) and simultaneously is the most reactive
tertiary amine. This amine application shortens the time of blowing through cores
even by 78% and the air blowing time by 54%, as compared to usually applied
amines: DMEA or TEA. This has a significant influence on the efficiency of devices
for the cores production, which grows – on the average – even by 30%. An increase
of a core box efficiency and a decrease of material consumptions provides signifi-
cant savings for foundry plants as well as improves the environment state. When
cores hardened by TMA are stored, the amine emission is reduced.
As a result of decreasing a carbon amount in silicate systems, a possibility of
lustrous carbon formation is by 20% lower than in case of using aromatic solvents.
Thereby, a tendency for forming defects related to lustrous carbon presence is
much lower.
Influence of the Cold-Box Technology on the Environment
A serious problem of the amine cold-box technology is the VOC emission during
the core production (mixing, shooting, storing) and during the mold pouring with
molten metal. At the beginning, there is vaporizing of remains of phenol and form-
aldehyde and solvents of higher boiling points. It is followed by the BTEX emission
and by the emission of other products of the binder thermal decomposition in work-
places and into the environment.
These harmful substances are partially condensed in inter-grain spaces and are
liberated after castings knocking out [7].
Three phases of the cold-box process, generating environment hazard, can be
singled out:
Phase I: as a result of high temperatures large solvent amounts, which are con-
tained in cores or molds, vaporize as well as phenol and formaldehyde, which –
as monomers – remained in resins due to not complete reaction.
Phase II: polyurethane chains are combusting in the reaction with oxygen con-
tained in molds and cores and on mold surfaces being in contact with the air. This
is a complete combustion.
Phase III: at a lack of oxygen or at its very small concentration, the pyrolysis,
i.e., thermal decomposition of organic substances or other binder components,
occurs. In dependence on temperature gradients and gas pressure in various
places of a core, organic substances can be: combusted, gassed, cracked, or con-
densed again. As the result of such process, new pyrolysis products such as
BTEX and CO, NOx, and other HAPs are formed. The temperature and the ratio
of the oxygen amount to organic substances in a mold and in cores are important
in the pyrolysis process. The binder fraction, geometry of a core and mold, ratio
of molding sand/metal, and temperature of liquid metal have an influence on the
pollutants emission.
The main source of the hazardous substances are solvents applied for resins and
polyisocyanate at the core preparation stage as well as during mold pouring with
liquid metal (binder thermal destruction) (Table 7.2). Therefore, from the very
moment of this technology implementation on the industrial scale (year 1968) up
to the present, works aimed at the selection of solvents (of resins and isocyanate),
the least harmful for the environment and employees, are carried out (Table 7.2)
Table 7.2 Chronological development of new generation of the cold-box process, with taking into
account the environment protection (Huttenes-Albertus)
1 Changes of aromatic solvents for rape seed oil, and due to this minimizing the
generation harmful substances emission at the cores production and during pouring with
molten metal (BTEX)
2 Application of the modified methyl ester of fatty acid in order to reduce the
generation emission of gases generated in the cores hardening process and in the molds
pouring process
3 Reduction of a free phenol content in resin, aimed at the improvement of storage
generation possibility of spent molding sands as well as further decreasing of harmful
substances emission (phenol permeation into underground waters)
4 Application of a solvent based on ethyl silicate in order to reduce the gases and
generation fumes emission after the molds pouring process
5 Development of the new generation of binders based on tetraethyl orthosilicate
generation (modified Si system). In this new generation, Si atoms are not only in a solvent, but
they are also integrated with resin particles. In comparison to aromatic cold-box
systems the carbon content was decreased by 23%, and the silica fraction in a
binder equals 12.4%
[15]. During the first period, solvents containing significant fractions of aromatic
hydrocarbons of high boiling points (e.g., naphtha) were applied. However, it
occurred that heavy aromatic hydrocarbons caused significant emissions of sub-
stances from the HAP group, when molds were poured with liquid metal. Therefore
solvents containing aromatic hydrocarbons were substituted by vegetable solvents
(aliphatic hydrocarbons). These were methyl esters of fatty acids (biodiesel). The
improvement of strengths and resistance to moisture content as well as reactivity of
binders were obtained, due to which the amine consumption decreased [16].
Emissions of harmful substances also significantly decreased. These new solvents
did not contain VOC, which reduced the BTEX emission [17, 18]. Vegetable sol-
vents are classified as incombustible substances, which makes their transport and
storing much easier.
The most efficient way of minimizing pollution emissions from molds, espe-
cially during their pouring with liquid metal, is the reduction of organic components
in molding and core sands. Therefore a successive important step in the develop-
ment of the amine cold-box technology was the introduction of silica–organic sol-
vents (instead of aliphatic solvents) (Fig. 7.6).
The application of this solvent constituted the first step in the development of
the cold-box technology of an inorganic character. The successive generation of
the TEOS-based binder (the so-called Si-modified system) was characterized by
the situation that Si atoms were present not only in a solvent but also in resin.
This happens due to the reaction of hydroxyl groups from resol resin with ethyl
silicate [13, 19].
TEOS is a flammable substance, sensitive to a moisture content. When it is not
protected against a moisture influence, it slowly hydrolyzes into SiO2 and ethyl
alcohol. At a temperature >600 °C, it decomposes, according to the reaction:
Fig. 7.6 Solvents applied aromatic solvent

in the cold-box technology CnH2n+1
in a historical perspective.
(Adapted from Refs. [13, n = 3 bis 14
14])
O
aliphatic solvent
C13-I C1019 – C
OCH3
tetraethyleneortosilicate (TEOS, CAS no 78-10-4)
C2H5
O
C2H5 O Si O C2H5
O
C2H5
Si ( OC2 H 5 )4 → SiO2 + 2 ( C2 H 5 )2 O
tetraethyl orthosilicate diethyl ether

This new binder is of a low viscosity, and therefore it is possible to use smaller
amounts of solvents. In effect, the BTEX emission significantly decreases, strength
increases, and the core knocking out improves. An increase of inorganic compounds
in a binder simultaneously limits a carbon fraction, and this – in turn – decreases
gases evolution rate from cores and significantly reduces CO2 emission. The
obtained binder is of a higher molecular weight and of a high thermal stability
[20–22] (Table 7.1).
Substitution of current organic solvents by modified ones caused a significant
reduction of unpleasant odors emitted by foundries [6] (Fig. 7.7) [23, 24].
The application of silicate acid ester as a solvent reduced the pyrolysis products
and odor emissions. In addition, due to a smaller carbon amount in a system, the
gases emission during mold pouring by molten metal was reduced by 20% as com-
pared to the classic cold-box technology. Further limitations of a negative influence
of the cold-box technology on the environment are only possible either by the appli-
cation of other solvents or by decreasing their amounts. Solvents applied for resin
(component 1) have especially large fraction (40–60%) in a binder. Lower amounts
of emitted hazardous gases mean a lower concentration of these substances in spent
Fig. 7.7 Comparison of odor emissions from the cold-box technology, measured at the hood stack
outlet in the aluminum alloys foundry. Both technologies (traditional and TEOS) contained equiva-
lent amounts of a binder. (Reprinted by permission from Refs. [23, 24])
OH OH OH OH OH OH
HO O OH HO O OH
n m n m
Fig. 7.8 Structure cold-box resin of the 5th generation. (Adapted from Ref. [13])
molding sands and thus less pollutions washed out into the environment. The appli-
cation of new technologies utilizing inorganic solvents causes a reduction of phenol
content in spent sands by at least 20%, and sometimes even by 50%, in dependence
of the fraction of cores made on a fresh sand (Fig. 7.8). In some cases the benzene
emission decreased by 66%. Simultaneously the binder fraction in a molding sand
was decreased by a few percent [13, 24–26].
Introduction of resin of the 5-th generation caused:
1. Reduction of OH− groups and thus:
–– Easier introduction of solvents
–– Lower resin viscosity
–– Decreasing of solvent amounts
–– Possible decreasing of isocyanate amount
2. Increase of molecular weight and thus:
–– Increase of thermal resistance
All these activities caused a reduction of hazardous substances emissions in each
stage of making cores and of molds (containing these cores) pouring with liq-
uid metal.
The results of the substances from the BTEX and PAH groups emitted from a
molding sand with resin from the cold-box technology, poured by liquid cast iron of
a temperature of 1350 °C (in a semi-industrial test), are shown in Tables 7.3 and 7.4,
respectively [27]. Among substances from the PAH group, naphthalene constitutes
the highest fraction. However, in the BTEX group was – in practice – only benzene.
Giese et al. [28] investigated the thermal decomposition mechanism of phenol–
urethane binder by means of the differential scanning calorimetry (DSC). Three
stages of the thermal decomposition of resin can be singled out on the obtained
curves. The first curve of an endothermic character in the range 70–115 °C corre-
sponds to vaporizing of solvents of low boiling points applied for resin. The succes-
sive curve within the range 170–320 °C is of an exothermic character and corresponds
to the thermal decomposition of carbonyl bond in the resin structure. In the final
heating stage, either changes of the structure of furan-urethane resin occur, or phe-
nol–urea molecules are changing into aromatic compounds. This happens in the
temperature range 320–420 °C [29].
In the above paper, the influence of the atmosphere character (oxidizing O2,
reducing CO, and neutral N2), in which the binder decomposition occurs, on a kind
and amount of substances from the BTEX group emitted from polyurethane binder
hardened by gaseous amine, was investigated. The TGA/DSC/MS technique was
applied. The highest amounts of HAP and VOC were emitted in the neutral atmo-
sphere. Changes into oxidizing and reducing atmospheres decrease amounts of
emitted HAP and VOC, whereas a production of lighter gases such as hydrogen,
water, and propane increases. When comparing reducing and oxidizing atmo-
spheres, the shifting of the BTEX emission toward higher temperatures, in the
reducing atmosphere without a noticeable quantity decrease, was found.
Work Environment
Producing of molds and cores – a control of amine consumption during a molding
sand hardening will assure that the emission of other potential volatile substances
will be negligible. Tertiary amines are used as catalysts. They have unpleasant
fishy odor.
Thermal decomposition of a binder – during a mold pouring by liquid metal,
apart from carbon oxide, other compounds (such as aromatic isocyanates, phenol,
and formaldehyde) should be monitored.
Isocyanates (MDI, TDI) are very toxic and irritating substances. They are char-
acterized by an exceptional chemical activity displayed in spontaneous reactions
with nearly all substances containing active hydrogen atoms. They act very toxic via
airways. They irritate eyes, airways, and skin causing allergy. The most dangerous
effects of the isocyanate toxicity are the results of breathing the air contaminated
with its vapors. The most often occurring symptoms are irritations of airways, run-
Table 7.3 Emission BTEX from cold-box technology

Content BTEX in emitted gasses (mg/g of the resin)
Volume of gasses (dm3/g resin) Benzene Toluene Ethylbenzene ∑Xylenes ∑BTEX
2.31 560 10.88 0 0.125 571
Table 7.4 Emission of PAHs from cold-box technology

Content PAHs (mg/g Content PAHs (mg/g
Name resin) Name resin)
Naphthalene 0.861 Benz(a)anthracene 0.313
Acenaphthylene 0.202 Chrysene 0.165
Acenaphthene 0.003 Benzo(b)fluoranthene 0.409
Fluorene 0.115 Benzo(k)fluoranthene 0.231
Phenanthrene 0.775 Benzo(a)pyrene 0.233
Anthracene 0.256 Indeno(1,2,3-cd) 0.320
pyrene
Flouranten 0.763 Dibenzo(ah)anthracene 0.067
Pyrene 0.693 Benzo(ghi)perylene 0.192
∑5.598 ± 0.556 mg/1 g resin
ning nose, cough, eyes irritation, and skin allergy. There are also certain, but lim-
ited, proofs of carcinogenic effects.
The basic preventing factor is a proper ventilation of rooms or working under
efficient fume cupboards. Working with isocyanates – kept in open vessels – should
be avoided. Rubber gloves and goggles should be worn at all operations.
Dust-protective clothes, protective gloves (e.g., of viton), safety boots, goggles
protecting against fine dusts (together with a half-mask), and equipment protecting
airways in a form of a half-mask together with filter-absorber should be applied.
Triethylamine (TEA) (CAS 121-44-8) is harmful when breathed. It can cause
irritation of airways. Contacts with its decomposition products can be dangerous for
health. Serious undesirable operations can be delayed in relation to the exposure
time. It causes serious defects of eyes and can cause burns of mouth, throat, or stom-
ach. Gloves and protective clothes should be worn. Goggles or face-protecting
devices should be used. Amine should be protected against heat sources, sparking
devices, open fire, and hot surfaces. Employees are not allowed to smoke. Electric,
ventilating, and lightening equipment of the explosion proof version should be
only used.
Dimethylethylamine (DMEA) (CAS 598-56-1) – highly flammable liquid and
vapor. Causes severe skin burns and eye damage. Harmful by inhalation. Skin con-
tact with all solvents should be avoided.
Dimethylisopropylamine (DMIPA) CAS (996-35-0) – highly flammable liquid
and vapor. Causes severe skin burns and eye damage. Harmful if inhaled. Corrosive
for the skin. Safety glasses, protective clothing, and gloves (PVC, neoprene) should
be used.
Trimethylamine (TMA) (CAS 75-50-3) – colorless gas of a fishy odor. It is harm-
ful via airways and after swallowing. Irritates airways and skin. There is a serious
risk of damaging eyes. Causes burns.
Dimethylpropylamine (DMPA) (CAS 926-63-6) may cause toxic effects if inhaled
or ingested/swallowed. Contact with substance may cause severe burns to skin and
eyes. Fire will produce irritating, corrosive, and/or toxic gases. Vapors may cause
dizziness or suffocation. Runoff from fire control or dilution water may cause pol-
lution. Flammable/combustible material. May be ignited by heat, sparks, or flames.
Vapors may form explosive mixtures with air. Vapors may travel to source of igni-
tion and flash back [26, 30].
7.3 A
lkaline Phenolic Methyl Formate Hardened
(BETASET)
This process was developed by the Borden Ltd. Company in Great Britain and
applied in the 80th of the previous century. On account of high costs, it is mainly
used for making cores. Alkaline phenol resol-type resin soluble in water, which
reacts with gaseous methyl formate, i.e., methyl ester of formic acid (HCOOCH3),
is applied in this process. As the reaction result the cross-linked macromolecular
binder and side products: methyl alcohol and potassium formate, are formed [4, 31].
Methyl formate is a hardener in this technology. It reacts with resin, and its residue
in a molding sand is very small. Therefore it is not necessary to perform the core
run-purge, which is needed when amine is used as a catalyst.
Methyl formate at a room temperature is liquid of a boiling point of 32 °C, but
undergoes gassing by means of the air heated to 80 °C, which simultaneously is its
carrier (Fig. 7.9) [3].
A core starts hardening before being taken out from a core box. In the initial
period, a core achieves 60–80% of the tensile strength value which it obtains after
24 hours.
Cores do not lose their properties even at a longer storage and can even obtain a
strength increase. Castings made in these molding sands do not have defects related
to lustrous carbon and veins. This technology can be applied for iron castings as
well as for steel castings. The process is characterized by rather unpleasant odor,
and the care is recommended since methyl formate is combustible. Resin is of a low
viscosity, which makes contacts with a matrix easier (Table 7.5).
Strength of cores produced by the BETASET technology are lower than pro-
duced by the cold-box amine technology, but higher than obtainable in the technol-
ogy of alkaline resol resins hardened by CO2, and in case of water glass
hardened by CO2.
This technology can be applied for alkaline sands (olivine, chromite) and for
high-silica sands. Into high-silica sand, 1.2–1.8% of resin is added while into zir-
conic sand 1.0–2.25%. In theory, the hardener consumption for total resin hardening
equals 20% of the resin amount. However, in practice, this consumption is higher
and equals 30–50%, in dependence of the core complexity. The system does not
contain nitrogen and sulfur and therefore can be used for the casting production of
spheroidal cast iron and of cast steel [4]. Protective coatings, hydrous or alcoholic,
which should be placed on well-hardened surface, can be used. During the mold
7.3 Alkaline Phenolic Methyl Formate Hardened (BETASET) 199
Fig. 7.9 Reactions during curing of the mold sands (BETASET process). (Adapted from Ref. [3])
Table 7.5 Physical chemical Viscosity at 25 °C (cps) 120

properties of resin used in
Density at 25 °C (g/dm3) 1.22
BETASET technology
pH 12.2
Content of solid parts (%) 60
Content of N (%) <0.5
Content of free formaldehyde (%) 0.5
pouring with liquid metal, the tensile strength of molding sands increases, under an
influence of high temperatures.
An additional advantage of this process is the fact that the installation does not
need to be so airtight, as in case of hardening by SO2 or by amines, since values of
allowable concentrations for methyl formate are much higher than for these
other gases.
Spent sands can be reclaimed by mechanical methods as well as by thermal ones.
Castings are easily knocked out, even castings of aluminum alloys.

Production of molds and cores – controlling of methyl formate concentration is
necessary, while concentrations of other harmful substances emitted in this process
are negligible. An odor emission is small [1].
Thermal binder decomposition – during a mold pouring with liquid metal, as a
result of the binder thermal decomposition, mainly phenol and formaldehyde are
emitted.
Protective, antielectrostatic clothes made of covered materials (e.g., vitone, neo-
prene) should be applied. Employees should also possess protective gloves (e.g., of
natural rubber or of neoprene); goggles protecting against dusts and drops of liquid
substance (together with half-mask); and protective equipment for airways: mask or
half-mask with the type A absorber [24].
7.4 CO2 Hardened Alkaline Phenolic
Traditional cold-box processes such as amine cold-box process and process of hard-
ening by SO2 or BETASET apply gaseous harmful substances – of unpleasant odor
and often toxic – as hardeners or catalysts. Therefore the cold-box process, in which
gases harmful for humans are not used, was developed.
A binder consists of two components:
• Phenol–formaldehyde resol-type resin, soluble in water; pH 14; viscosity 300–
700 mPa∙s; free phenol content <0.05%; free formaldehyde content <0.1%; and
resin addition equal 2–2.5%. Resin contains also boric acid, borate, and other
additions.
• Oxyanion, which is able to form a durable complex with resin in a weakly alka-
line environment
• CO2 gaseous as a hardener
Water-soluble alkaline phenol resin, resol type, is mixed with sand and then
hardened by gaseous CO2. The cross-linking resin reaction (hardening) is induced
by CO2. Carbon dioxide – introduced into a molding sand – forms with water car-
bonic acid and decreases pH value of a solution, which initiates the cross-linking
reaction. This reaction proceeds with a participation of complex-forming factor
(oxyanion) present in a resin solution. The durable complex is formed and a binder
is hardened [4, 32]. The hardening reaction rate depends on a temperature, pressure,
CO2 flowing rate, and sand temperature. A preliminary hardening occurs in the core
box, and then in 24 hours the molding sand strength increases as a result of a further
cross-linking of resin and evaporation of water. Cores are obtaining the tensile
strength a little lower than cores produced in the cold-box amine process or in
BETASET. In order to obtain a comparable strength, the higher additions of a binder
are required, which increases production costs. Therefore the application of this
technology is limited.
7.4 CO2 Hardened Alkaline Phenolic 201
Research performed by Liu W. et al. [33] concerning the development of a new

binder indicated that an addition of NaOH as a catalyst, at maintaining the molar
ratio of phenol/aldehyde = 1.0: 2.5, introducing 15% of silane as a cross-linking
agent and introducing an active agent (in a form of an organic compound) allows to
obtain, under optimal conditions, directly after blowing through by CO2, the mold-
ing sand of a compression strength (R0) 2.0 MPa which increases after 24 hours
(R24) to 4 MPa. A fracture of bridges, joining sand grains when organic active
substance is added to resin, is typically cohesive [33]. Cores produced in this tech-
nology have very good thermal properties. Fresh molding sand should be stored
under a cover, since it will be hardened on the surface under an influence of CO2
contained in the air (Fig.7.10). On the other hand, ready cores should be stored in
dry places. Protective coatings – hydrous or with other solvents of alkaline charac-
ter – can be used [4, 32, 34].
Resin does not contain nitrogen, sulfur, and phosphorus, which eliminates cast-
ing defects related to the presence of these elements. Veins do not occur, and the
possibility of catching carbon is small. On account of a highly aggressive environ-
ment (pH = 14), the applied equipment should be made of the selected materials
(alloyed steels, gray cast iron, carbon steel, vinyl polychloride). Sands of neutral pH
and of a low acid demand should be used as matrices. These can be high-silica
sands, zirconium, and chromite sands. Their moisture content must be below 0.1%
and binding agent up to 0.2%. Olivine sand is not suitable. An optimal sand tem-
perature 15–30 °C.
This technology is especially suitable for producing large cores and molds for
cast steel castings and aluminum alloys castings.
This molding sand is advantageous in respect of ecology. It does not contain com-
bustible components and of an unpleasant odor. The emission of gases, during a
molding sand preparation, mold pouring, and casting knocking out, is rather low.
During a molding sand preparation, only CO2 is emitted, while at mold pouring with
CH2
O O
B
–
ONa O O
HO HO
K + CO2 + H2O CH2
HOH2C CH2OH + B CH2OH
Na+ K2CO3
HO HO
CH2OH CH2OH
alkaline phenol resole oxygen anion complex
Fig. 7.10 Resin cross linking after CO2 introduction (resole–CO2 process). (Adapted from Ref.
[3])
liquid metal, small amounts of benzene and CO2 are emitted [34]. On account of
this, neither special equipment for purifications of gases nor scrubbers for their
absorption are required.
Molding sands from this technology are difficult for reclaiming. Only CO2 is
emitted during the core production. Therefore there is no need of installing expen-
sive systems for the environment protection. However, during mold pouring with
molten metal and castings, knocking out gases from the BTEX group, mainly ben-
zene, can be emitting. The results of emissions of substances from the BTEX group,
from the mold poured with liquid cast iron of a temperature of 1350 °C and with
liquid aluminum alloy of a temperature of 680 °C, are presented in Table 7.6.
The results of emission of substances from the PAH group from molding sands –
obtained in this technology – poured with molten cast iron of a temperature of
1350 °C, in the “semi-industrial” test, are presented in Table 7.7, respectively [27].
According to [35] the emission from a molding sand with alkali phenol resin
hardened by CO2 was investigated in two stages:
Stage I: contained molding sand mixing, making, and storing cores.
Stage II: pouring (with molten cast iron of a temperature of 1449 °C), cooling,
and knocking out. This emission was several times smaller than in case of the
technology with phenol–urethane resin hardened by amine (PUCB).
7.5 SO2 Hardened Epoxy/Acrylic (Free Radical Curing)

(FRC)
This process has several advantages such as good compatibility of a molding sand,
long work time, and good mechanical properties. Molding sands do not contain
nitrogen, phenol, nor formaldehyde; they are well knocking out, and cracks on cast-
ings are not formed. However, on account of its costs, this technology is seldom
applied.
The main feature of this process is not a resin type but cross-linking bases. Resin
hardening occurs in this process by means of free radicals. Resin has to have double
bonds between carbon atoms: polyester resin–acrylic resin, polyester resin–ure-
thane resin, or polyester resin–epoxide resin. These resins usually have small
molecular weight and are soluble in organic solvents nearly up to 50%. Resins are
Table 7.6 Emission of BTEX from resole–CO2 process, pouring with molten cast iron and
aluminum alloy
Volume of gasses Content BTEX in emitted gasses, mg/g of the mold sand
Alloy (dm3/kg) Benzene Toluene Ethylbenzene ∑Xylenes ∑BTEX
Cast iron 21.673 317.9 23.2 0.2 4.1 345.4 ± 34.5
Aluminum 4.4 11.6 2.9 0.05 0.2 14.75 ± 1.5
alloy
References 203
Table 7.7 Emission of PAHs (resole–CO2 process), poured with molten cast iron
Concentration (μg/kg of the Concentration (μg/kg of the
Name mold sand) Name mold sand)
Naphthalene 3.8 Benz(a)anthracene <7.1
Acenaphthylene 44.1 Chrysen <3.4
Acenaphthene 2.0 Benzo(b) <0.7
fluoranthene
Fluorene 4.8 Benzo(k) <0.4
fluoranthene
Phenanthrene 9.3 Benzo(a)pyrene <0.6
Anthracene 14.3 Indeno (1,2,3-cd) <0.8
pyrene
Flouranten 29.8 Dibenzo (ah) <0.6
anthracene
Pyrene 22.1 Benzo (ghi) <0.6
perylene
∑PAHs 144.2
±28.8
mixed with organic peroxide MEKP (methyl–ethyl ketone peroxide C8H16O4),

which initiates a reaction. A molding sand is hardened by SO2, introduced in a
stream of a carrier gas, e.g., CO2 or N2.
After, the blowing through the run-purge – by means of the same gas which was
used as a carrier gas – is always performed. This process is aimed at the removal of
not reacted sulfur dioxide from a matrix.
Resin (1.2–1.4%) is mixed with sand, and such mixture is then blown into the
core box and blown through by gaseous SO2 (25–60% versus resin). The system
does not contain nitrogen [2]. The application of dangerous SO2, limits possibilities
of a wider industrial implementation of this technology.
References
1. Archibald JJ, Warren DW (1989) Productivity and ecology considerations when selecting a sas
cured binder system. Am Foundry Soc Trans 97:311–322
Woburn
pojiv, Brno
4. Lewandowski JL (1997) Materials for foundry moulds. AKAPIT, Krakow (in Polish)
6. Pilato L (2010) Phenolic resins : a century of progress. Springer, New Jersey
7. Krause J, Davis W (2011) 5 Tips to minimize amine use and reduce pollution. Mod Cast
101:36–39
8. (2010) US 2010/0126690 A1 (Patent)
9. Kroker J, Wang X (2014) Advancements in cold box gassing processes. In: 71st World Foundry
Congress, Bilbao, pp 1–4
10. Archibald JJ, Robinson ML (1994) Recycling amine catalysts: a pollution prevention tool.
AFS Transactions, 102:555–558
11. Boenisch D, Lotz W (1985) Causes for unexpected losses of strengths of cold box cores.
Giesserei Prax 72:83–88
12. Drożyński D (1999) Surface phenomena in the molding sands binding process in the classic
cold-box technology. AGH University of Science and Technology (in Polish)
13. Serghini A (2010) Cold-box silicon systems – can they reach a peak? Foundry J Polish
Foundrymen’s Assoc 5–6:220–234 (in Polish)
14. Serghini A, Bieda S (2003) Improved, ecological polyurethane cold-box process. Foundry J
Polish Foundrymen’s Assoc 53:224–230. (in Polish)
15. Sipos MM (2012) Cold – box –herze mit verbrennungsförderenden additiven zur reduktion
emissionen und kondensaten. Giesserei Prax 12:525–529
16. Lewandowski JL (2000) Development trends of cold-box processes. Foundry J Polish

Foundrymen’s Assoc 50:134–136 (in Polish)
17. Alexander I (2010) Politece high reactivity PUCB binders. Foundry Trade J 184:138–139
18. Trinowski DM, Ladegourdie GM, Löchte K (1999) Löchte new coldbox binder system for
improved productivity. Am Foundry Soc Trans 107:51–57
19. Groning PM, Strunk D (2011) The cold –box process a bridging technology. Cast Plant
Technol 1:14–18
20. Holtzer M, Górny M, Kmita A (2017) The influence of motorisation on the climate warming.
Int J Glob Warm 11:495–514
21. Schrey A (2009) Emissionsreduzierete PUR-cold-box-binder. Giesserei Prax 96:56–58
22. Svidro JT, Dioszegi A, Svidro J, Ferenczi T (2017) The effect of different binder levels on
the heat absorption capacity of moulding mixtures made by the phenolic urethane cold-box
process. J Therm Anal Calorim 130:1769–1777
23. Serghini A Structurally modified cold-box systems with improved properties. Huttenes –
Albertus GmbH Dusseldorf, Germany. http://metkoha.com/documents/Structurally_modi-
fied_CB_systems_with_improved_properties.pdf. Accessed 16 Aug 2019
24. Huttenes-Albertus Company, GmbH and HA International (2016) www.ha-international.com.
Accessed 16 Aug 2019
25. ASK Chemicals (2017) https://www.ask-chemicals.com/home.html. Accessed 16 Aug 2019
26. Sander V, Neun W, Poetzsch M (2017) Cast part manufacturer introduces new cold box tech-
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29. Giese SR, Shepard A (2014) Understanding emissions characteristics of a foundry sand binder.
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pp 309–311
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Foundry Soc Trans:1007–1012
Chapter 8
Heat Curing Processes
8.1 Linseed Oil Oven Bake
This is probably the oldest process, in which chemically bound molding sands are
utilized. This technology is easy for the application and resistant to veins and cracks.
It is mainly used for producing the selected small cores.
Some natural oils, such as linseed oil, undergo polymerization and hardening as
a result of the air or heat influence.
High-silica sand is mixed with an appropriate oil, often with a dextrin addition
and a few percent of water. Oil additions equal from 0.8% to 4%, dextrin app. 2%,
and water 0.5–2% of the sand mass. Originally only linseed oil, colophony, and
turpentine were applied, but presently various oils are used. It is also possible to
introduce additions speeding up the drying process. Currently, oil binders constitute
mixtures of the so-called dry oils with resins and solvents. Synthetic dry oils are
produced in the reaction of glycol or glycerol (glycerin) with fatty acids. Typical
chemical structure of the obtained product is presented below (Fig. 8.1):
Hardening occurs as a result of cross-linking of unsaturated fatty acids contained
in oils. It is initiated by oxygen from the air and sped up by heating in an oven at
temperatures from 190 to 260 °C, for 1–2 hours. Cores achieve their tensile strength
of 1.34 Pa. Strengthening of bonds can be obtained due to mixing resin with dry oil.
Phenol, urea–formaldehyde, and alkyd resins are applied. Since resin–oil mixtures
are often of a high viscosity, using of solvents is necessary.
When cores are drying, unpleasant odors are emitted, and therefore ovens should
be ventilated. During their thermal decomposition, oils and resins used in oil bind-
ers probably will not have a negative influence on the environment [1]. Locke and
Ashbrook [2] analyzing the composition of gases generated during the thermal
decomposition of oil binder found the presence of CO, CO2, oxygen, nitrogen,
hydrogen, and a few alkanes (CnH2n+2).

206 8 Heat Curing Processes
Fig. 8.1 Structure of O

cross-linked of unsaturated
fatty acids
CH2 OC ( CH2 )7 CH=CHCH2 CH = CH (CH2 )4 CH3
O
CH OC ( CH2 )7 CH=CHCH2 CH = CH (CH2 )4 CH3
CH2 OC ( CH2 )7 CH=CHCH2 CHCH2 (CH2 )4 CH3
OH
8.2 Warm-Box Process
The warm-box technology is very similar to the hot-box technology; it uses the
same hardening techniques. It differs only in the kind of the applied resin, which
allows the core hardening at lower temperatures 130–180 °C. However, this resin is
much more expensive than the one applied in the hot-box technology. Therefore the
warm-box process, in spite of several advantages, is not often applied.
A binder is based on furfuryl alcohol, with its typical content being app. 70%, or
with solid polymer of this alcohol, of a low nitrogen content. Copper salts with
aromatic sulfonic acids in aqueous or alcohol solution are catalysts. A characteristic
feature of these catalysts is their excellent stability in an ambient temperature and a
relatively low dissociation temperature being 150–170 °C. Due to that the instru-
mentation temperature can equal 180 °C, which leads to significant energy savings,
up to 15–25% as compared with the hot-box process.
A mixture of sand, resin (1.0–1.3%), and hardener (20–30% versus resin) is
blown into the warmed core box. A catalyst is activated under the heat influence and
the binder is hardened. A hardening time equals 10–30 seconds, and the obtained
final tensile strength reaches up to 3.0–4.0 Pa.
Apart from the mentioned above, the advantages of the warm-box technology as
compared to the hot-box technology are (Fig. 8.2):
• Emission decrease
• Lower requirements concerning core boxes
• Good work time of a molding sand
• Good fluidity of a molding sand
• Dimensional stability of cores during transporting and storing
• Good knocking out of cores
• Good quality of casting surfaces
Preparation of molding sands and instrumentation used for core production by
means of the hot-box method can be utilized in the warm-box technology. The
essential difference concerns the lower temperature needed for molding sand hard-
ening, which increases a production efficiency.
8.2 Warm-Box Process 207
Fig. 8.2 Comparison of volumes of gases emitted at a temperature of 800 °C from molding sands
prepared according to the hot-box and warm-box technologies. (Reprinted by permission from
Ref. [3])
To defects of the warm-box technology can be counted [4]:

• decrease of molding sand fluidity as compared to the shell process;
• relatively high costs of a binder and catalyst;
• in the case of thick-walled cores, the hardening time is much longer;
• limited storage time of cores, especially at a high humidity of the air.
Foundry plants producing for the motorization needs were especially interested
in this technology, which could substitute so far applied the hot-box process or the
Croning shell process.
Striving to achieve the environment-friendly binder, the warm-box method of
cores production called the Cleantech process (Hüttenes-Albertus) was developed.
Three-component system is used in this process. It contains (1) urea–formaldehyde
resin modified by a natural reversible polymer, in order to assure the thermal stabil-
ity of the system in an aqueous solution and to reduce the liquid metal penetration
and core deformation, (2) hydro salt as a catalyst, and (3) gas in the hot air stream [5].
This molding sand does not contain phenol, polyisocyanate, and solvents of plant
origin or from the crude oil processing. A formaldehyde emission is below 1 ppm.
Main components of a binder are liquids of a low viscosity, due to which they are
easily coating sand grains. The core box should be warmed to app. 30 °C, in depen-
dence on the core shape and warming system. A temperature increase causes reorga-
nization of particles in resin, and formaldehyde is evolving. It immediately reacts
with a catalyst producing sulfuric acid, which initiates the resin polymerization. This
cycle is repeated until the whole resin or catalyst is used. A stream of hot air
(110–160 °C) blown through the core box helps the reaction proceeding and removes
a humidity excess from the core. 1.5–2% of resin and 0.3–0.4% of catalyst – versus
the matrix mass – is added. The core achieves the required strength properties after
25 seconds of the hot air blowing. Organic substances contained in a molding sand
cause that this sand can be already reclaimed at a temperature of 500 °C. The obtained
reclaim is of pH = 6.8 and can be applied in other alkaline processes. The TGA analy-
sis residue (carbon) constitutes 25%, similarly as in the cold-box amine technology.
The largest difference between the cold-box amine process and the Cleantech
technology is the fact that at temperatures above 450 °C, a solvent evaporates from
the cold-box binder while polyurethane is still stiff and generates veins, contrary to
the Cleantech technology.
The special advantage of the warm-box technology is a low emission of gases
during the core storing (app. 5–10 times smaller than in the cold-box process) and
casting producing. As an example, at a temperature of 800 °C, the emission of sub-
stances from the BTEX group from molding sands obtained in the warm-box tech-
nology is a few times smaller than from molding sands obtained in the cold-box
technology [5]. One of the versions of the warm-box technology is the vacuum
warm-box process. This process allows to produce cores hardened already at tem-
peratures 70–100 °C [6]. Especially tight core boxes, in which a pressure can be
decreased, are applied. Decreased pressure allows to remove gases – directly from
the core box – and to subject them to conventional processing. Under a vacuum
condition, solvents and water are vaporizing very fast, decreasing pH value, which
initiates a hardening process even at a relatively low temperature. Phenol resole and
furan resins in combination with a special hardener (containing, e.g., copper chlo-
ride (II)) are used as binders, in this version of the warm-box technology [7–9].
8.3 Hot-Box Process, Phenolic or Furan-Based
Cores of a high dimensional accuracy and of good mechanical properties can be

produced in this technology, but to achieve this, very good knowledge and control
of the production process are required. These process limitations constitute its costs,
mainly of resin, energy, and pattern-related instrumentation. This hot-box process is
an extension of the shell-forming process. It differs from it, by three elements: is
applied only for the core production, full cores are made, and the bonding reaction
is exothermal [10]. Cores produced by this technology can be used for producing
castings of gray cast iron, light metals, and heavy metals.
A wide range of resins can be applied in the hot-box technology:
• Urea–formaldehyde UF
• Urea–formaldehyde–furfuryl UF–FA
• Phenol–formaldehyde PF
• Phenol–formaldehyde–furan PF–FA
• Urea–formaldehyde–phenol–formaldehyde UF–PF
Most often phenol–formaldehyd novolak resin type is used with additions of

aqueous solutions of modified ammonia hydro salts as a catalyst, sometimes with
urea addition to reduce the free formaldehyde content [10, 11]. However, only heat-
ing of a system causes irreversible hardening. Other additions are also applied:
silanes, iron oxides, and silicon oil.
8.3 Hot-Box Process, Phenolic or Furan-Based 209
Liquid phenol–formaldehyde resin and a catalyst are preliminarily mixed with

sand (in practice, high-silica sand of a minimal content of clay and dust fractions).
Such mixture is shot into the heated core box, where it is hardened (core box heat
transfer hardener components into a gaseous state) for app. 5–60 seconds in depen-
dence on the kind of resin, thickness of core walls, and molding sand composition.
In the case of thin cores, this time equals 5–10 seconds, while for cores of a
thickness of 50 mm, the hardening time can reach 60 seconds. The final tensile
strength of cores equals 1.4–2.8 Pa. They should be stored in a dry atmosphere. The
core box temperature varies from 180 to 240 °C. At an excessive heating of instru-
mentation, the hardening time abruptly shortens, and the core surface can be burned,
which will cause the core brittleness during the mold pouring with liquid metal. The
bonding reaction is exothermic, which favors further core hardening, after taking it
out from the heated core box.
The resin addition is within the range from 1.2% to 3.0% of the sand mass, at the
average fraction being 1.8%. The catalyst fraction changes from 10% to 25% of the
resin mass (most often it is 20%) [7, 8]. Resin contains 6–12% of N, and since cata-
lysts are usually ammonium salts which also contain nitrogen, the total nitrogen
content in the system equals 10–14%, in dependence on the applied resin [12].
Admittedly systems not containing nitrogen – or containing its very small amount –
are available, but obtainable cores are not of such good quality as in the case of
using resins containing nitrogen. Significant acceleration of the hardening process
in the core box is obtainable due to the catalyst addition (Fig. 8.3). These are organic
or inorganic salts of strong acids (e.g., ammonium nitrate (V)). Sometimes Fe2O3 is
added to protect against pinhole formations in steel castings and in castings of sphe-
roidal cast iron.
Phenolic resin
or
Silica sand
Urea-furan resin Hardener (NH4NO3)
(1.4 % - 2.0 %) (0.3 % - 0.5 %)
Core shooter
Mixer (200-260 °C for 4-120 s)
Hardening out of hot-box
Fig. 8.3 Scheme of the hot-box process: core making. (Adapted from Ref. [7])
Cores produced in this technology are used for iron castings (phenol resole res-
ins), aluminum castings (urea–furfuryl resins), and steel castings (phenol–formal-
dehyde resins). This process is especially recommended for the serial core
production, in which the accuracy and reproducibility of dimensions and shapes as
well as the proper strength and knocking out ability are required. Hydrous coatings,
which are then dried, are placed on hardened cores. Cores produced with phenol
resin undergo a small widening during a mold pouring with liquid metal, which can
cause their deformation. In the case of aluminum alloy castings, special resins,
which are easily decomposing at temperatures of molds pouring with these alloys,
are applied.
A molding sand applied in the hot-box technology is cheaper than the one used
in the shell process, more kinds of resins can be used, and the hardening process is
faster. However, fluidity is worse, and lifetime is limited, and the consumption of
core sand is higher (only full cores are produced by this method).
The newer version of this technology is the hot-box plus process. Humid sand is
mixed with phenol–formaldehyde resole resin and a hardener, such as in the tradi-
tional process. The hardener contains additionally hexamethylenetetramine
(HMTA), which under the temperature influence decomposes into ammonia and
formaldehyde, and this formaldehyde is cross-linking resin forming strong
bonds [13].
Reaction pathway of resin hardening in the hot-box plus process is shown in
Fig. 8.4. An essential advantage of the hot-box plus technology is especially long
lifetime as compared to the traditional hot-box process [10].
Furan resin applied in the hot-box process is polymerizing according to the
scheme, shown in Fig. 8.5. There is no need of introducing additional reagents. The
only reaction is condensation, in the result of which methylene bridges (-CH2-) are
formed between rings and water is liberated.
Properties of urea–furfuryl resin and a catalyst applied in the hot-box technology
are presented in Table 8.1.
OH OH OH
CH2 CH2 CH2 CH2
CH2 CH2
n heat
OH
+ CH2 CH2
N
OH OH
N N HTMA
N
Fig. 8.4 Scheme of the curing of PF novolak resin in the hot-box plus process (HTMA –
hexamethylenetetramine)
8.3 Hot-Box Process, Phenolic or Furan-Based 211
CH2 OH H CH2 OH
O O
H CH CH2 OH
O O
Fig. 8.5 Scheme of the curing of furfuryl resin in the hot-box process
Table 8.1 Properties of urea–furfuryl resin and a catalyst applied in the hot-box technology [13]
Parameter Resin Catalyst
Viscosity at w 20 °C (MPa·s) 350–500 –
Density at 20 °C (g/cm3) 1.25–1.30 1.18–1.21
Content of the free furfuryl alcohol (%) Max. 35 –
pH 7.5–8.0 3.5–5.0
The advantages of the hot-box technology of producing cores are [4]:

• High production efficiency
• High dimensional accuracy and good quality of surfaces of final castings
• Low costs of final processing of castings
• Good formability of cores in molds
However, there are also disadvantages:
• Limited working time
• Necessity of using metal instrumentation
• Fumes emission
During the hardening of cores made with phenol–formaldehyde resin, formalde-
hyde is evolving, and due to that, the place of core production as well as the nearest
surroundings must be well ventilated, and efficient fume exhaust systems should be
provided. Direct contacts of skin with liquid resin and molding sand should be
avoided.
The substitution of hexamethylenetetramine by trimethylphenol as a hardener
decreases the emission of unpleasant smells during the mold pouring with molten
metal and increases the molding sand strength.
Table 8.2 Emission of gases from molding sand made in the hot-box technology (PF resin +
hardener + HMTA)
Volume of Emission of gases (mg/ kg mold sand)
gases
(dm3/kg
Sample mold sand) Benzene Toluene Ethylbenzene Xylenes
Mold sand pouring with molten cast 20.00 7.57 0.66 0.004 1.85
iron (temperature 1350 °C)
Mold sand pouring with molten 1.890 19.90 10.86 0.15 4.52
AK11 alloy (temperature 750 °C)
The results of semi-industrial tests of the gas evolution rate from a molding sand,
made in the hot-box technology, at pouring with liquid cast iron (of a temperature
of 1350 °C) and with liquid AK11 alloy (of a temperature of 750 °C), are shown in
Table 8.2. In the case of pouring with cast iron, ten times more gases are evolving
from a molding sand than at pouring with aluminum alloys. However, at a lower
temperature, more substances from the BTEX group are generated than at a higher
temperature [7–9].
8.4 Croning Process (Shell Process)
This process (patented in 1944 by J. Croning, as a process of producing molds and

cores) is the only one, out of all processes of producing molds and cores, in which
coated sands ready for usage are delivered directly from the producer to the foundry
plant [10]. The coating process can be also performed in the foundry.
The Croning process consists of two stages:
• Production of sands coated by phenol resin novolak type and hexamethylenetet-
ramine, hot or warm
• Hardening of cores or shell molds in the warmed core box or on the pattern plate
Production of Coated Sands
One of the methods of producing coated sands is the hot coating. In this process
granulated phenol–formaldehyde, novolak type resin of a melting temperature app.
80–100 °C, is applied. 2–3.5% of this resin (versus a mass of sand and in depen-
dence on the application) is added to a sand heated up to a resin melting tempera-
ture (120–150 °C). Then resin is melting and coating sand grains. Aqueous solution
of HMTA (25–40%) is applied as a hardener. After cooling the coated sand is
blown into the heated core box or on the heated pattern plate (up to a temperature
of 230–260 °C), covered by a divider, in result of which resin is melted and then
hardened.. Hexamethylenetetramine decomposes at a temperature of 160 °C into
two basic components: formaldehyde and ammonia. When the coated sand is in
contact with the heated pattern, formaldehyde is cross-linking resin creating a
strong bond. After the molding sand layer of the needed thickness is formed, the
8.4 Croning Process (Shell Process) 213
excess of not bound molding sand is removed, and – in addition – the produced
shell is heated to a temperature of 350 °C for its final hardening. Admittedly, resin
does not contain free nitrogen, but it is in hexamethylenetetramine (40%).
In another production method of coated sands (the so-called warm coating),
hexamethylenetetramine is added into cold or slightly warmed sand (60–90 °C) fol-
lowed by calcium stearate, and then after a short mixing, phenol–formaldehyde
novolak resin in alcohol solution is introduced and again mixed. During this mixing
alcohol and water are evaporating (blowing of warm air can be additionally applied).
The mixture in an agglomerating form is supplied on a shake out grid with a sieve
and cooled. The hardening process proceeds in the same way as in the case of hot
coated sands. Calcium stearate is added shortly before the mixing end [13].
In the shell process, a molding sand is either deposited on the pattern plate
(heated up to temperatures of 230–260 °C) or is introduced into the warmed core
box, covered with a divider.
Cores can be full or empty with not hardened molding sand inside. This not hard-
ened sand can be removed from a core by turning it “upside down” and used again.
The hardened molding sand forms a “shell,” and from this feature comes the name
of the process. Usually shell molds have wall thicknesses of 20–25 mm.
This technology warrants a high dimensional accuracy (dimensional tolerance
±0.1 mm) and good final surface of castings, good knocking out ability, and easy
removal of cores. The storage time of coated sands is – in practice – unlimited. Due
to the application of synthetic resins of a high strength, the core deformation as well
as the need of their strengthening by the so-called core reinforcement is eliminated
[10, 15]. Certain limitations in a wide application of this process constitute the price
of coated sands and of pattern instrumentation. Therefore this technology is mainly
applied for making small and medium cores and molds in the mass casting produc-
tion. Steel castings, light metal alloy castings, copper alloy castings, and certain
kinds of cast iron castings can be produced by this technology.
A negative feature of this technology application is a segregation of the sand
mixture with powdered resin during making molds and cores. To prevent this effect
appropriate additions are introduced into a molding sand, e.g., kerosene, but this
decreases strength and causes a need to increase the resin addition to 5–6%. In
effect the price is higher, and gas emission increased.
As a matrix of sands coated with resin mainly high-silica sand is used, it has a
significant dilatability and limited abilities of heat conduction. In order to obtain the
maximum strength at a minimal resin amount, sand must be clean and grains
rounded and free from surface contaminations. Therefore zirconium sands, less
often chromite sands, are used. The resin hardening process starts from pH lower-
ing, which is obtained by adding phosphoric or maleatic acid. Also acidic salts, e.g.,
aluminum sulfate or urea phosphate, can be added. Aluminum sulfate reacts with
formaldehyde forming hexamethylenetetramine and sulfuric acid. It should be men-
tioned that the only presence of hexamethylenetetramine in a molding sand does not
cause its bonding and it is necessary to warm the mixture to the appropriate tem-
perature for hardening.
An excess of HMTA causes too high hardening, resin becomes brittle, and its
resistance to moisture content decreases. A higher reactivity and higher cross-
linking density can be obtained by increasing the ratio of formaldehyde to urea. On
the other hand, free formaldehyde is harmful to the employees’ health.
Sand coated with resin has a very long lifetime as long as it is stored in a dry
atmosphere and not subjected to too high temperatures, which could cause an
agglomeration of grains.
The hardening time of molding sand equals approximately 2 minutes, the longer
time the thicker shells are formed. A temperature increase only negligibly acceler-
ates the hardening process. The application of protective coatings is not necessary
since the achieved final surface is of a high quality. Casting knocking out ability is
good and the dimensional accuracy and reproducibility of details very good.
Therefore, despite the fact that this process is relatively slow and costly, it is applied
in the case of high requirements concerning dimensional accuracy, surface qual-
ity, etc.
Disadvantages of the hot-box technology are, among others, the necessity of
using instrumentation made of metal, relatively high material costs, limitations in
sizes of produced cores, and fume emissions.
Spent molding sand is well reclaimed by the thermal method.
Substitution of HMTA by trimethylphenol improves properties of coated sands.
The resin reactivity is increased, and the nitrogen content in a molding sand
decreases. Nitrogen present in coated sands can cause an increase of defects in steel
castings. Therefore, efforts to have as low as possible nitrogen content should be
undertaken.
During the urea–formaldehyde resin hardening, formaldehyde and ammonia are
emitting to the environment, and therefore efficient ventilation of places where
cores and molds are produced is necessary. Formaldehyde can be also liberated
from hardened resin, especially when this resin is in the acidic environment. During
mold pouring with liquid metals and, later, during cooling, unpleasant and harmful
gases are emitted. Therefore often shell molds are cooled in closed tunnels, where
there is a possibility of catching these gases and – after cleaning – reliving them into
the atmosphere. Introduction of trimethylphenol is favorable for the environment
since the emission of harmful substances is reduced.
References
1. Bates CE, Scott WD (1977) Decomposition of resin binders and the relationship between the
gases formed and the casting surface quality. Part 3. AFS Trans 85:209–226
2. Locke C, Ashbrook RL (1950) Nature of mold cavity gases, a review. Am Foundry Soc Trans
58:584–594
3. Gardziella A, Pilato LA, Knop A (2000) Phenolic resins. Chemistry, applications, standardiza-
8.4 Croning Process (Shell Process) 215
4. Westwood GW (1985) The cast for heat-cured molding and core making processes. Foundry
Trade J 158:512–516
5. Vargas M (2014) Clean technology: a innovative organic binder for aluminium and iron cast-
ing. In: 71st World Foundry Congress (WFC 2014), pp 1004–9
6. IQU (1981) The vacuum warm box process. EP 00 44 739 A1
8. Mark HF (ed) (2014) Encyclopedia of polymer science and technology, 4th edn. Wiley,
New York/Chichester
9. Lewandowski JL (1997) Materials for foundry moulds. AKAPIT, Cracow (in Polish)
10. Kilarska J, Solarski W, Zawada J, Zieliński E (1990) Chemistry of binders for moulding and
core sands. Publishing House AGH (in Polish)
11. Brown J (2000) Foseco ferrous Foundryman’s handbook, 11th edn. MA Foseco International,
Woburn
12. Shi Y, Wang L, Han Y, Liao C, Xie L, Yang C (2016) Curing reaction and mechanism of phe-
nol–formaldehyde novolac resins for foundry. China Foundry 13:205–210
13. Huttenes-Albertus Company, GmbH and HA International (2016) www.ha-international.com.
15. Dahlmann M (2004) Resin coated sands. Foundry J Polish Foundrymen’s Assoc 6:507–513.
(in Polish)
Part III
Inorganic Binder Systems of Molding and
Core Sands and Protective Coatings
Assuming as the dividing criterion of binders their chemical character, it can be

stated that there are organic binders (where synthetic resins or natural polymers are
the most often used) and inorganic binders.
The inorganic binder notion, in the molding and core sand technology, is related,
first of all, to water glass and to binders based on modified water glass. However to
this group belong also cement, phosphates, geopolymer binders, inorganic salt
(NaCl and KCl)-based binders (for core sands), and green sands [1]. Sometimes
green sands, i.e., molding sands with bentonite which is a natural inorganic binder,
are considered as a separate group, next to molding sands with inorganic binders
and with organic binders. Their “greenness” is related to their weakness and plastic
condition, contrary to dried molds of the extreme hardness and stiffness.
On account of increased requirements concerning the environment protection
and improvements of work conditions in foundries, molding sands with inorganic
binders – especially with water glass – are getting importance and finding applica-
tions in several technologies of molding and core sands. In these technologies either
irreversible gelling reactions (being the result of carbon oxide or ester influence) or
reversible reactions (based on dehydration of hydrated sodium silicate in hot-box
and warm-box processes or in the microwave heating process) are utilized. Water
glass-based binders belong to the oldest binders applied in foundry processes. The
use of carbon dioxide as a sodium silicate hardener for molding sands was patented
by Petrzela of Czecho-Slovakia in 1947 [2]. Numerous technologies of molding and
core sands on sand matrices, where sodium silicate – subjected to various modifica-
tions – was a binder, were developed.
Regardless of a significant progress within the molding sands area, especially
with synthetic resins, still more than 70% of cast iron castings is done in green sands
with additions generating lustrous carbon [3], being fully aware that these sands are
harmful for the environment and employees.
The main directions of investigations concerning molding sands with inorganic
binders – for molding sands with water glass – are an improvement of its knock-
ing out ability and compliance for the mechanical reclamation, limitations of
organic components, utilizing physical factors for binder hardening, as well as the
218 Part III Inorganic Binder Systems of Molding and Core Sands and Protective Coatings
possibility of reducing binder amounts [3, 4]. For molding sands with bentonite
(green sands), the main problem constitutes the selection of additions generating
lustrous carbon, which would be less harmful for the environment, as well as the
bentonite reclamation from knocked out sands.
References
1. Polzin H (2012) Anorganische Binder. Fachverlag Schiele & Schön GmbH,
Berlin
2. Petrzela L (1947) CSR – patent no. 81931. Water glass CO2 process.
Czechoslovakia. (in Czech)
3. Howden JD (2014) Green sand “less is best” a more sustainable philosophy for
change. Proceedings of 71st World Foundry Congress, 19–21 May, Bilbao,
Spain
4. Polzin H (2009) Anorganische chemische Binder. Giesserei 69:74–76
Chapter 9
Sodium Silicate Molding Sands
Hydrated sodium silicate (popular name “water glass”) is utilized as a binder of

molding sands from the middle of the previous century. Molding sands with water
glass belong to the group of environment-friendly molding sands [1]. Water glass
substituted, in several cases, binders based on linseed oil or crude oil products. This
significantly contributed to the work environment improvement due to decreasing
of emissions. Hydrated sodium silicate is applied in molding and core sand tech-
nologies in which irreversible gelling reactions occur, as a result of carbon dioxide
or esters influence, or reversible reactions of dehydration of hydrated sodium sili-
cate in the hot-box or warm-box process or by microwave heating [2–4]. For many
years, in practice, two molding sand technologies using water glass as a binder were
utilized: sands hardened by organic esters (liquid hardener) (self-setting technol-
ogy) and sands hardened by CO2 (cold-box technology). However, on account of
certain unfavorable properties of these sands, they were to a significant degree dis-
placed by molding sands with organic binders [2–4]. Undoubted advantages of
sands with water glass as a binder are a lack of unpleasant smells, small emission of
fumes during molds pouring, no emission of harmful substances, and a good sus-
ceptibility of cores. In addition, the price of molding sands with hydrated sodium
silicate is lower than molding sands with organic binders.
Sands with sodium silicate have worse knocking out ability than sands with
organic binders (which – in case of cores – causes problems), weaker reclamation,
significant sensitivity to moisture, short bench life, and lower cohesive strength of
bridges joining matrix grains. Lately, due to more severe requirements of the natural
environment protection, sodium silicate as a binder has a period of a certain renais-
sance [5, 6]. In order to eliminate or limit unfavorable properties of sands with
sodium silicate, they are subjected to modifications by organic or inorganic com-
pounds, or hardening by means of physical agents is applied. Physical–chemical
parameters of sodium silicate, especially high-silica sand, such as wettability and
cohesive strength, significantly influence the molding sand strength, contributing –
at the same time – to the knocking out improvement. In consequence of these opera-
tions, the addition of sodium silicate can be reduced.

220 9 Sodium Silicate Molding Sands
A hardening of binders in molding sands with sodium silicates is traditionally

done either by a mixture of liquid organic esters or by CO2 blowing through.
Technologies of sands with water glass hardened by physical factors (e.g., heating),
up to now not much used, are presently finding more and more applications. The
hardening factor, due to the dehydration process, is the heat originated from the core
box and hot air blowing through cores [3, 4, 7–9]. Such hardening method, as com-
pared to classic methods, has several advantages, e.g., economic, being the result of
the decreased energy consumption (even up to 100 times), decreased binder addi-
tion (2.5–1.5%), and shortening the hardening process (even 100 times) [3, 10]. In
addition, decreased binder additions cause decreasing the final compression strength
(Rctk) and improving the reclaimability of molding and core sands. An application of
microwave heating caused a decrease of (Rctk) of sands by app. 1/3, as compared with
the sand with water glass hardened by a mixture of esters [10, 11].
Aggravating regulations concerning the environment protection force foundry
plants to reduce the fraction of molding sands with organic binders. Due to high
strength parameters of molding sands with water glass thermally hardened and their
small harmfulness for the environment, they can become the competition for sands
with organic binders.
Presently the following technologies are being developed for molding sands with
water glass thermally hardened: INOTEC® (ASK Chemicals Company) [12],
CORDIS® (Hüttenes-Albertus Company) [13], and AWB® (Minelco Company) [14,
15]. Data concerning the tensile strength of molding sands with water glass and
molding sands with organic binders after various hardening time are listed in
Table 9.1.
In the case of cores with inorganic binders based on sodium silicate, their small
resistance to humidity constitutes the problem. The hardening reaction of sodium
silicate (e.g., by dehydration caused by increased temperature) is – to a large
degree – reversible. In dependence on atmospheric conditions occurring in foundry
plants or in storage places of mold sands and cores, the inversion of the silicate
cross-linking process can occur, and – as a result – cores or molds are losing their
strength and are damaged (e.g., cracking) faster [16]. This can be prevented by the
core storage in dry places, but this is not always possible under foundry plant
Table 9.1 Comparison of the tensile strength of molding sands with sodium silicate (inorganic
binder) thermally hardened and molding sands with organic binders in dependence on hardening
time and humidity
5 min 2 (h) 24 (h) 24 (h) humidity
Kind of binder MPa
Organic binder 1 0.48 0.61 0.61 0.59
Organic binder 2 1.59 1.62 2.25 0.20
Inorganic binder 1 1.89 2.43 2.10 0.87
Adapted from Refs. [13–15]
9.1 Sodium Silicate: Structure and Physical–Chemical Properties 221
conditions. Therefore presently, in sands with inorganic binders based on sodium

silicate, special additions are applied (the so-called activators), which signifi-
cantly delay the reaction inverse to the silicate cross-linking and cause these sands
to be more humidity resistant [17].
9.1 S
odium Silicate: Structure and Physical–Chemical
Properties
Sodium silicate is obtained by melting high-silica sand with alkaline carbonates at

a temperature of app. 1450 °C (Fig. 9.1). Sodium silicate can occur as a solid or as
silicate binder dissolved in water – “water glass.”
A general form of hydrated sodium silicate, which is a salt of a weak silicic acid
Si(OH)4 and strong base NaOH, can be written as follows:
mNa 2 O ⋅ nSiO2 ⋅ xH 2 O
In its water solution, the equilibrium of the sodium silicate hydrolysis stabilizes
(Fig. 9.2):
The basic structural unit in the chemical structure of sodium silicate is silicon
cation Si4+ surrounded by four oxygen anions O2−, which are forming
tetrahedron.
Neutral silane groups (–Si–O–H) and alkaline (–Si–O–Na) groups occur in water
solutions of sodium silicate. Since sodium silicate in water solution indicates
strongly alkaline reaction, mainly (–Si–O–Na) groups occur. In water solution these
groups react, e.g., with water (hydrolysis) forming silane groups (–Si–O–H) – this
is the activation process of water glass (Fig. 9.3).
These silane groups are very reactive and undergo a condensation reaction with
water separation (Fig. 9.4). This happens due to changes of the system external state
(e.g., by dehydration) where shifting – from the chemical equilibrium in the direc-
tion of increasing particles – occurs.
ONa ONa
T T
SiO2 + 2 Na2CO3 NaO Si ONa HO Si OH + Na2O
– 2 CO2 +H2O
ONa ONa
hydrolysis
Fig. 9.1 Preparation of sodium silicate. (Adapted from Refs. [1, 18])
2(Na2 O • nSiO2 ) + 2(2n + 1)H2 O = 4NaOH + 2nSi(OH)4
Fig. 9.2 The reaction of hydrolysis of sodium silicate

ONa ONa
NaO Si ONa + H+ OH– NaO Si OH + Na+ OH–
ONa ONa
Fig. 9.3 Reaction of sodium silicate activation. (Adapted from Refs. [1, 18])
ONa ONa ONa ONa

NaO Si ONa + HO Si ONa NaO Si O Si ONa + H2O
ONa ONa ONa ONa
Fig. 9.4 The condensation reaction by dehydration. (Adapted from Refs. [1, 18])
ONa ONa
ONa ONa ONa ONa
NaO Si O Si ONa
Si O Si ONa NaO Si O Si ONa
ONa O
ONa ONa ONa ONa
NaO Si ONa
ONa
Fig. 9.5 Increase of sodium silicate particles by multiple condensation – formation of spatially
branched chains. (Adapted from Refs. [1, 18])
As the condensation reaction progresses, water is displaced from the lattice and
multimolecular silicates are formed (dimers, trimers, etc.) in accordance with reac-
tion equations, which contain new siloxane bonds –Si–O–Si–, forming gel [18]
(Fig. 9.5).
Siloxane bonds –Si–O–Si– can become decomposed in water and in alkaline
solutions, and as a result, smaller particles are formed (Fig. 9.6).
Reactive silane (–Si–O–H) groups in strongly alkaline environments are forming
salts containing (–Si–O–Na) groups, which are not active (Fig. 9.7). This leads to
deactivation of water glass (Fig. 9.7).
In the case when the system is not influenced by external factors, the water glass
state remains without changes. pH of the system plays a significant role in the “con-
densation” process. The condensation rate is the highest at pH 6–7 and clearly drops
when the pH value either decreases or increases. In strongly alkaline solutions (at
pH app. 13) and strongly acidic (at pH app. 2–3), the condensation rate is very
small. pH of the sodium silicate solutions is usually high (hydrolysis of the salt of a
strong base and weak acid), and therefore in these solutions, condensation does not
occur – no deposit is emitted.
According to K.R. Iler [19] (Fig. 9.8) at pH < 7, the polymerization reaction
occurs by putting in order of lattices (scheme A), which are joining each other,
forming gel. This reaction rate is low. At pH > 7 the polymerization reaction is
much faster, and its course is in the direction of the gel structure formation
(scheme B).
9.1 Sodium Silicate: Structure and Physical–Chemical Properties 223
ONa ONa ONa ONa

NaO Si O Si ONa + H+ OH– NaO Si OH + HO Si ONa
ONa ONa ONa ONa
Fig. 9.6 Decomposition reaction of sodium silicate as a result of the siloxane (Si–O–Si) bond
hydrolysis. (Adapted from Refs. [1, 18])
ONa ONa
NaO Si OH + NaOH NaO Si ONa + H2O
ONa ONa
Fig. 9.7 The reaction of deactivation of sodium silicate. (Adapted from Refs. [1, 18])
Fig. 9.8 Stages of monomer polymerization and particle formation according to R. K. Iler [19]
Figure 9.8 shows the stages of growth of the silica structure elements according
to R. K Iler [19].
According to [8, 19, 20] hydrolyzed sodium silicate is a colloidal solution
containing micelles SiO44− negatively charged, dispersed in water with adsorbed
on their surface alkaline ions of an opposite sign (Na+) and water layers:
Helmholtz–Stern layer (adsorption layer) and diffusion layer. The simplified
micelle model is shown in Fig. 9.9. Micelle forming during a water glass produc-
tion is related to characteristic features and properties of silicates. Their structure
is symbolically called “crystalloidal” or “colloidal.” According to authors [8,
Fig. 9.9 A simplified model of the micelle. (Adapted from Ref. [21])
18–20, 22] ions Na+, H+, and OH−, as well as silicate anions of the type
[(xSiO3ySiO2zH2O)]2− (of various polycondensation degrees), are present in the
water solution of sodium silicate. SiO2 molecules adsorb on their surfaces
[SiO3]2− anions, forming this way the nucleus of a micelle of a negative charge.
Due to that, it has the ability to attract H+ cations forming micelles with the
electric double layer, in which the Helmholtz–Stern adsorption layer (internal)
contains ions of opposite signs (H+, [SiO3]2−). The diffusion layer (external) is
built by hydrogen cations H+ situated in the sphere more distant from the nucleus
and of much weaker interactions between ions. The further from the micelle
nucleus, the weaker the interaction forces between ions. At the Helmholtz–Stern
and diffusive layer boundary, the slip plane is formed, in which the additional
electrokinetic potential (called zeta potential) is created.
Apart from water being in the electric double layer, “free” water is present in
the intermicellar solution. Micelles formed in such way have constant electro-
static charge causing their mutual repelling and the stability of the sodium sili-
cate colloidal solution [18, 19, 22].
Hydrolyzed sodium silicate is a colloidal solution containing micelles and inter-
micellar solution [8, 18–23]. A micelle consists of a nucleus and the solvation layer,
which includes two layers: Helmholtz – Stern layer (adsorption layer) and diffusion
layer (Fig. 9.9). The nucleus contains SiO2 and silicate anions. The solvation layer
consists of: Na + and H2O molecules. The sodium ions present in this layer and in
the intermicellar solution are hydrated. Water glass properties depend on its chemi-
cal composition: kind and amount of basic oxide Na2O, colloidal system state (vis-
cosity, pH), and its modulus Ms [3], expressed by dependence (Eq. 9.1):
9.2 Hardening of Molding Sands with Sodium Silicate 225
x mol SiO2
MS = ⋅ 1.0323 (9.1)
y mol Na 2 O

Water glass of a module from 2 to 2.9 and density 1330–1550 (kg/m3) [3] is
the most often applied in the foundry industry. The value of module decides on
the binder quality. The larger the module, the higher the viscosity of sodium sili-
cate at the same density. As it is well-known, this parameter – apart from other
factors – influences the degree of water glass spreading on matrix grain surfaces.
For the assessment of water glass usefulness as a binder, its coagulation thresh-
old (CT) is important. This threshold is defined as the minimal amount of elec-
trolyte (acid), which causes clear coagulation of the water glass solution [3]
defined by (Eq. 9.2):
CT = 0.31VA [%Na 2 O ] (9.2)

where:
VA (ml) – consumption of HCl at concentration of 1 mol/l
9.2 Hardening of Molding Sands with Sodium Silicate
Regardless of the applied hardener (gaseous or liquid), the factor providing strength
of molding sands is silica gel formed as the sol coagulation result (Fig. 9.10). The
water glass coagulation process proceeds as the H+ ion concentration in the intermi-
cellar solution is growing.
The water glass hardening process can be:
• Irreversible (chemical hardening): hardening by the influence of CO2 or by a
mixture of esters
• Reversible (physical hardening): hardening by dehydration, e.g., drying by warm
and hot air (warm-box, hot-box), and hardening by microwaves [20, 23]
9.2.1 Molding Sands Hardened by Chemical Agents
Sodium Silicate/CO2 System

This process has several advantages: is cheap, easily applicable, natural, and work
environment-friendly. However, it has also several disadvantages: weak compact-
ibility, weak mechanical properties, small resistance to humidity, and bad reclaim-
Fig. 9.10 Scheme sol ↔ gel transition coagulation

Si(OH)4sol Si(OH)4gel
peptization
ing ability. These unfavorable features cause the increase of casting costs and the
decrease of interest in this technology [3, 24].
Cores are obtaining their full strength only after drying. Cores produced with
using sodium silicate hardened by CO2 do not obtain the theoretically obtainable
maximum strength, since water is not completely removed from a binder. This fact
decreases the possibility of applying this technology in automated lines. Therefore
it finds the application mainly in small casting houses in unitary and batch produc-
tions of castings of medium and large dimensions, regardless of their complexity, as
well as in the core production.
In this process sodium silicate water solutions (water glass) of a module 2.0–2.8
are used. Water glass in amounts 2–4% is mixed with sands and blown through by
carbon dioxide, which is of a weak acidic character. The CO2 fraction should not
exceed 1–2% parts by mass of sand, and blowing through time should be from 10 to
60 min. Cores are usually made in the shooting machines. Under the CO2 influence,
the sand hardening occurs in a short time. The surface hardening reaction by means
of CO2 is also essential at other hardening methods [3, 24].
The silicate binder reaction with carbon dioxide (CO2) [3, 25, 26] is shown
(Eq. 9.3):
Na 2 O ⋅ nSiO2 + 2 nH 2 O + CO2 → Na 2 CO3 + nSi ( OH )4 (9.3)

The final hardening of water glass occurs in a moment of the mold pouring with
liquid metal. The supplied heat causes a fast removal of physically bound water due
to which the over-wetted zone of a smaller strength is formed. In mold zones, being
at some distance from the cooling casting, the sand strength increases again causing
the growth of the final compression strength Rctk, which makes difficult the casting
knocking out from the mold. In addition, molding sands with water glass are losing
their cohesive and adhesive strength after hardening and became brittle and hygro-
scopic. This significantly influences durability of molds and cores, limiting the pos-
sibility of their storage. A large drawback of these sands is the mechanical
reclamation difficulty [3, 25–28]. On account of the above, it is important to lead the
binder hardening process to the “finish,” e.g., by CO2 hardening.
Modifying additives (e.g., saccharine) decrease a resistant of these sands to
overdrying. As the result of processes occurring in mold layers being in a direct
contact with the casting surface (cast iron or cast steel), the molding sand is
strongly heated (usually over 800–900 °C) [24, 29–34]. This is the reason that the
silicate binder – during cooling – is transforming into the vitrified sand of a very
high strength, causing difficulties in its knocking out. At a certain distance from
the casting surface, where the molding sand is not fully hardened, due to the mold
warmed by liquid metal, the activation of the hardening process occurs once
more. This causes the strength increase and – in consequence – worsening of the
knockout property. The classic pathways of the final compression strength
changes (Rctk), characteristic for sands with sodium silicate, are presented in
Fig. 9.11.
Fig. 9.11 Changes of the 5

final compression strength II max.
(Rctk) at the temperature
The final compression

increase: molding sand 4
strength Rctk, MPa

with sodium silicate
hardened by CO2.
(Adapted from Refs. [3,
3 I max.
35])
2
0
0 200 400 600 800 1000
Temperature, °C
The application of various additions to water glass (e.g., aluminosilicates)

improves knockout abilities of sands and causes less sensitivity to moisture.
Additions of some kinds of dissolved sugar [36, 37] protect sodium silicate from the
second strength maximum (above 800 °C). However, too large sugar addition can
cause an increase of released volatile organic compounds (VOCs).
Sodium Silicate/Organic Ester System
Molding sands with sodium silicate hardened by a mixture of esters, at a room tem-
perature (the so-called self-setting sands), are currently finding the most intensive
application out of all molding sands with inorganic binders (of course, apart from
sands with bentonite) for producing foundry molds and cores.
As a hardener of these sands, the mixture of esters is usually used, e.g., glyc-
erin and ethylene esters, and first of all glycerin mono-, di-, and triacetate and
glycol diacetate, the addition of which amounts usually to 10%. Esters are
organic compounds, which are formed in the esterification reaction of acids with
alcohols.
The main advantage of applying esters as water glass hardeners is the possibility
of decreasing the amount of water glass added to sands by app. 50% (only 2.0–3.0%
of water glass is added), as compared to other water glass-based sands. This favor-
ably influences decreasing the final strength of sands made in this technology [23].
Utilizing hardeners of various gelling rates, it is possible to control directly the
sands’ lifespan. Molding sands made in this technology are applied mainly in cast
steel foundries for making large- and middle-size castings at low- and middle-
serialized production.
The mechanism of bonding water glass in molding sands, in which the mixture
of esters is used as a hardener, can be divided into three stages:
• Ester hydrolysis in the alkaline solution of sodium silicate and the formation of
acetic acid and ethylene glycol (Fig. 9.12a)
Fig. 9.12 Mechanism of bonding of hydrated sodium silicate in the esterification process accord-
ing to [3] (a) ester hydrolysis, (b) dissociation of acetic acid, and (c) reaction of acetic anions with
sodium silicate. (Adapted from Refs. [3, 38])
• Dissociation of acetic acid (Fig. 9.12b)

• Reaction of acetic anions with water glass (Fig. 9.12c)
Hydrated sodium acetate, formed in the water glass hardening process with using
the mixture of esters, negatively influences processes of the wet as well as dry rec-
lamation of molding sands (plastifying of molds and cores) [23].
The strength of molding sands with water glass directly depends on the primary
strength of silicate gel [3]. External parameters such as humidity and temperature of
a gaseous phase influence the sodium silicate dehydration. This process is compli-
cated and depends also on internal parameters of the system: module, viscosity, and
a binder density.
In the literature [39] observed five temperature intervals for the silicate binder
of module Ms from <2.5–3.5>, in which its rheological properties are changing
Fig. 9.13 Changes of the 3.5

final compression strength I max. II max.
(Rctk) at the temperature 3
The final compression

increase: molding sand
2.5
strength, MPa
with sodium silicate
hardened by esters.
(Adapted from Refs. [3, 2
35]) 1.5
1
0.5
0
0 200 400 600 800 1000
Temperature, °C
due to dehydration. The first interval is at 100 °C, in which the water loss is the
largest and equals app. 40% (sodium silicate transfers into elastic or semielastic
state). In the second stage, the water loss equals from 15% to 25%, and a hard
amorphous film occurs. In the third stage when the water loss is from 10% to 12%,
this film becomes spongy and brittle. In the fourth interval, at further heating to
temperatures 200–250 °C, the film is swelling and becomes light. In the last, the
fifth heating stage to temperatures 600–800 °C and then cooling, the film becomes
hard and anhydrous.
The described stages of a binder dehydration occur in molds and cores after
pouring them with liquid casting alloys. They are responsible for the knocking out
mechanism of sands with sodium silicate, since the characteristic maximal final
compressive strength occurs approximately near 200 °C and near 800 °C (Fig. 9.13)
[20, 23].
A majority of authors [3] attribute the occurrence of the I maximum of the final
compression strength Rctk to the binder dehydration process, at which the most
important is dehydration of not bound sodium silicate. The II maximum strength
Rctk occurring at a temperature of app. 800 °C is probably caused by melting of
dehydrated sodium silicate.
9.2.2 Molding Sands Hardened by Physical Factors
The implementation of the process utilizing sodium silicate hardened by CO2 con-
stituted the turning point in the yield of the core production process. The succes-
sive stage, resulting from the higher and higher requirements concerning quality
and complexity of cores, was the implementation of organic binders hardened by

means of heating or by gases. These technologies were characterized by better
strength of cores, stability of their storage, and production yield than of cores
produced with sodium silicate hardened by CO2. These facts caused a drop of
interest in this technology. However, higher and higher social awareness concern-
ing the environment and natural resources protection, as well as the air, water, and
soil pollution, forced the binder producers to develop new technologies with the
application of less harmful substances and forced the foundry managers to develop
more effective environment protection systems. All these caused a significant
increase of the casting production costs [24, 33]. Alkaline solution of sodium sili-
cate or binders formed on its base (modified sodium silicate) hardened by thermal
factors are materials fulfilling the above requirements.
In these methods, during dehydration, water glass transfers into anhydrous glassy
silicate film, which binds matrix grains. The hardening process can be shown by the
following reaction (Eq. 9.4):
Na 2 O ⋅ nSiO2 ⋅ xH 2 O + Q → Na 2 O ⋅ nSiO2 (9.4)

where: n, x – stoichiometric coefficients.
INOTEC® Process
The INOTEC® technology (ASK Chemicals) [12, 40] was created as a result of a
continuous development of technologies based on inorganic binders. The INOTEC
system is the new, 100% inorganic – free from emissions – binder variant based on
water glass, dedicated to the casting production, especially of aluminum, non-
ferrous metals alloys, and cast iron.
This binder consists of three components: liquid mixture of silicates (1.8–2.5%),
highly mineralized activators (0.1–1.0%), and, if necessary, mineral material
(1–30%) added to high-silica sand. These components can be mixed in various pro-
portions in dependence on the producer’s requirements. During the casting produc-
tion, no fumes are generated. The INOTEC® system can be utilized at the production
of engine blocks and cylinder heads. Apart from visible advantages for the environ-
ment, the INOTEC® technology is competitive due to technological properties of
molding and core sands as compared with traditional technologies based on water
glass. The binder hardening occurs due to dehydration in the heated core box and
the core blown through by the hot air of a temperature 180–200 °C. Technological
advantages of the INOTEC® technology:
• Decrease of the molding sand adhesion to the casting surface
• Improvement of the molding sand knocking out ability, easy removal of cores
from castings
• Excellent dimensional accuracy of castings
• Increased thermal stability of molds and cores
• Possibility of applying water protective coatings
Fig. 9.14 INOTEC® binder composition. (Adapted from Ref. [41])
All these constitute an undoubted advantage of this technology over technolo-

gies based on organic binders. At the application of special activators, the core
can obtain the hot strength >2 MPa, which warrants optimal conditions for its
transport (Fig. 9.14). High requirements of customers concerning the casting
surface quality are able to fulfill molding sands with organic binders. It is pos-
sible due to forming of the lustrous carbon layer on the casting molding sand
boundary, which constitutes a barrier against the liquid alloy penetration deep
into the mold. Therefore, in order to achieve the same surface quality in sands
with inorganic binders, various additions, e.g., of substances worsening the wet-
tability of sand cores surfaces, are introduced.
The INOTEC® technology is both cheap and ecological, which causes that it
constitutes the alternative to molding and core sands based on organic binders.
At first the cores from the INOTEC® technology were used in the production of
permanent molds of brass. These castings were made without protective coatings of
permanent molds, and the obtained surfaces were of very good quality. Advantages
of this technology are also small emissions of gases, lack of unpleasant smells, and
the time saving at equipment cleaning.
CORDIS® Process
CORDIS® (reserved sign by Hüttenes-Albertus International) is the inorganic
binder, in which the only solvent is water [13, 42–44]. This binder is composed
of the modified aqueous solution of sodium silicate and the pulverized addition
named Anorgit. In dependence on the binder type, its matrix consists of the com-
bination of phosphate, silica, and borate groups. Properties of the given binder
type can be controlled by the aimed combinations and changes of the matrix
structure. Inorganic additions are used for improving binder properties. By the
combination of all these additions, important properties of sands such as fluidity
or durability of cores during their long-term storage, can be controlled. The
molding sand containing CORDIS is shot into the core box heated to a tempera-
ture of 120–160 °C, in dependence on the core geometry. The hardening process

is irreversible and constitutes a combination of the dehydration and chemical
reaction. When a molding sand is introduced into the core box, a preliminary
hardening of a sand occurs, and the external shell is formed on the core. This
stage contains hardening obtained only due to drying and of a purely physical
character. In addition, in dependence on the applied CORDIS binder, the chemi-
cal hardening process can be initiated, and in result the core strength can
be higher.
Since, during the hardening, burning processes do not occur; there is no emis-
sion of BTEX and amines as well as unpleasant smells. The CO2 emission is sig-
nificantly reduced, because microwaves of a small power are used for the final
hardening. In this technology water glass is hardened in a purely physical way, by
means of water evaporation. Molding sands hardened in this way are character-
ized by very good strength properties in the initial hardening phase as well as after
24 h, both in a highly humid atmosphere and in the dry air. Thus, it can be con-
cluded that the physical hardening process very favorably influences the quality of
the prepared sand. The so-called softening of the sand external layer does not
occur during the storage (water absorption, binder hygroscopicity, not complete
binder hardening), which often occurs in the case of molding sands with water
glass hardened by esters. Protective coatings, both aqueous and alcoholic, can be
applied, but a small strength drop can be expected.
An additional good point of sands from the CORDIS® technology is their very
good knocking out property, as compared to other technologies, which – in the
case of classically produced sands with water glass – constitutes one of their larg-
est drawbacks. On account of its good susceptibility, this binder can be applied
for producing cores of highly complex shapes, e.g., water jackets. In dependence
on the applied sand and CORDIS® binder, the addition of binder is from 1.5% to
3.0%. Such cores obtain the cold bending strength from 3.5 to 5.5 MPa. During
the mold pouring with liquid metal, neither fumes nor unpleasant smells are
evolving. Gases can be evolved for a very short time. The comparison of emis-
sions from Cordis sand and from sands produced in other technologies is shown
in Fig. 9.15.
Fig. 9.15 Comparison of the condensate volume for the CORDIS® binder with other binders
(temperature of liquid aluminum alloy: 700 °C). (Reprinted by permission from Ref. [13])
Table 9.2 Parameters of cores made by various technologies

Technologies
Parameters Inorganic binder Cold-box Coated sands
The flexural strength Rg on cold (MPa) 3–5 3–5 4–20
Loss on ignition (%) 0.2–0.28 1–1.8 1.6–5.5
Gas emissivity (ml/g) 3–5 8–15 8–28
In the case of aluminum castings, there is no need of applying protective coat-

ings on cores, but both kinds of coatings, water and alcohol, can be applied. A
special attention should be directed to storing of cores with inorganic binders.
Since these binders are of a hydrophilic character, they are susceptible to humidity,
and therefore cores should not be stored for too long in places of a high humidity
[45]. The basic parameters of a few processes of making cores are shown in
Table 9.2.
AWB® Process
The AWB® technology (developed by the Minelco, Nemak Dillingen, and Audi
Company) [14, 46] is applying modified water glass of a decreased viscosity. Due
to this a binder can be mixed easier and homogenized with a molding sand. The
obtained molding sand viscosity is similar to the one of sands from the cold-box
technology. The molding sand hardening occurs as a result of a physical water
removal, which is performed in two stages. In the first stage, the hardening occurs
in the core box (warmed to temperatures: 140–200 °C), which is connected with the
vacuum pump for the water vapor removal. After app. 10–60 s, in dependence on the
core size and shape, the hardened shell is formed, strong enough to make possible
taking out the core from the core box and its transport. The final hardening is per-
formed by microwaves of a weak power. This stage is very important, since water
remained in the core can dissolve binder bridges which shortens the storage time.
Binding of sand grains occurs by silicate bridges (Fig. 9.16). This process was
developed for making engine blocks of aluminum alloys. Due to this, the energy
consumption was decreased by 30%, and emissions of greenhouse gases, wastes,
and sewages were highly reduced. Molding sands made in the AWB technology are
easily knocked out. These cores were verified at producing castings of cast steel,
cast iron, and non-ferrous metal alloys. Investigations indicated that, in order to
achieve the same strength of cores made in the AWB technology as cores made in
the cold-box technology (resin:activator = 0.8%:0.8%), the application of 2.5% of
the AWB binder was necessary.
SOLOSIL TX Process
The SOLOSIL TX binder (name reserved for FOSECO) is the inorganic thermoset-
ting binder, based on water glass, of properties comparable to organic binders and
environment-friendly. This binder consists of two components: solution of modified
sodium silicate (app. 2% of a module of 2.0–2.4) and fine powder containing vari-
ous minerals [47, 48].
Fig. 9.16 Schematics of bond formation by AWB® binder. (Reprinted by permission from
Ref. [15])
The hardening occurs in the core box heated to 150 °C. An introduction of
appropriate additions into a binder significantly improves the cores strength. The
strength increase is caused not only by the physical (thermal) hardening of sodium
silicate but also by decreasing the humidity level caused by this addition. Apart
from the composition, the amount of these additions is very important. Additions
introduced into the binder, apart from their ability of the core dehydration, decrease
the wettability of liquid metal vs. mold and decrease the binder viscosity, which
causes a fluidity increase of the core sand. Apart from the physical (temperature)
hardening of the binder, the chemical reaction of reactive SiO2 also occurs in
sodium silicate and in some mineral components of the addition. At the total dehy-
dration, the core maximum strength is achieved, but precautions should be taken
to avoid brittleness of cores caused by their overdrying. The introduced mineral
additives have also to prevent the chemical and physical penetration of liquid
metal into the sand depth. The production of cores based on sodium silicate matrix
should be characterized by as short as possible cycle time to achieve yields of the
sands with organic binders. This time is determined by the cores drying stage. For
its optimization (e.g., hot airflow flux, core box temperature) the computer simula-
tion is used.
The SOLOSIL TX binder does not contain organic additions, and due to that
during the mold pouring, no unpleasant smells are emitted (only water vapor) [48].
9.2.3 Sodium Silicate Modification
The sodium silicate modification is performed to limit its unfavorable properties

and to improve some others. It comprises physical and chemical modifications [49].
Physical Modification
The physical modification of hydrated sodium silicate concerns mainly produc-
tion conditions of the primary material, which is the silicate sodium glaze and
concerns a temperature and conditioning time (keeping for the determined time in
a temperature above the melting temperature). According to [8, 22] the best struc-
ture homogeneity characterizes hydrated sodium silicate subjected to thermal
conditioning for 1 h. On the other hand, the most advantageous properties related
to the final strength had water glass conditioned for 1.5 h. The physical modifica-
tion is utilized in the case of the “aging” of sodium silicate in time, causing a loss
of its homogeneous polymerization degree. Along with the flow of time, it
becomes the mixture of orthosilicate and large colloidal particles, which decreases
the binding force by app. 20–30%. This process can be stopped by influencing
water glass by, e.g., strong magnetic field, by ultrasounds, or by warming it in the
autoclave. The effect of the performed procedures is rehomogenization of the
water glass polymerization, due to which the binder recovers the lost binding
properties [11, 29, 32].
Chemical Modification
The chemical modification of sodium silicate is related to changes of its structure
and properties caused by chemical reactions occurring under an influence of sub-
stances introduced into the polymer matrix. As a result of the chemical modifica-
tion, it is possible to achieve 70% increase of the binding force.
Modification by Morphoactive Organic Compounds
One of the ways of improving properties of water glass as a binder is the introduc-
tion of morphoactive organic compounds into its structure. Soluble in water high-
molecular substances with active functional groups, such as −OH, −NH2,
=CONH, −CONH2, and −COOH, and others, can be modifiers. Polymers and
acrylic copolymers, polyalcohol, cellulose derivatives, polyphosphates of linear
or branched structures, etc., belong to this group. An introduction of morphoac-
tive modifiers into the pulping process of silica sodium glaze causes the colloidal
structure formation. Modifiers accelerate this process, favor formations of stron-
ger cohesive bonds, and decrease the molding sand brittleness. Their introduction
into the hydrated sodium silicate increases efficiency of its operation as a binder
and allows to decrease its fraction in the molding sand [8, 9, 20, 50].
For the chemical modification of sodium silicate, high-molecular components,
e.g., polyphosphate, polyacrylamide, polyvinyl alcohol, or carbamide, diversified in
respect of a molar mass, kind and amounts of functional groups, and polymerization
degree [50], are applied.
Modification by Ultrafine Powders
One of the newer modification methods of sodium silicate is the introduction of
“ultrafine powders” of inorganic laminar aluminosilicates, containing exchangeable
ions Mg2+ and Al3+ (of the particle size from 0.2 to 3 μm), into its structure. As the
result an increase of the binding power at simultaneous decrease of the final strength
Rctk (by app. 35%) was achieved [51, 52].
Modification by Nanoparticles
A constant development of new technologies, including nanotechnology, creates
possibilities of using still smaller particles; it means nanoparticles, for the water
glass modification. Nanoparticles, according to a general definition, are particles
of which at least one dimension is smaller or equal 100 nm (1 nm = 10−9 m). They
are characterized by unique physical, optical, chemical, electrical, and technical
properties [8]. Namely, substances generally considered to be safe in the macro
scale can – in the nanometric form – be dangerous for humans and act, e.g., as
poisons.
Hydrated sodium silicate as a molding sand binder was modified by nanoparti-
cles of metal oxides (ZnO, MgO, and Al2O3) in various solutions (methanol, etha-
nol, propanol) [52–57]. As the performed investigations indicate the water glass
modification by the mentioned nanoparticles significantly influenced physical-
chemical as well as mechanical properties of molding sands.
The model of the modification proceeding of hydrated sodium silicate, by means
of nanoparticles in dependence on the temperature, was developed.
(a) At an ambient temperature: the modification mechanism of sodium silicate
causing the increase of the tensile strength Rmu of molding sands contains the
following stages:
• Chemisorption of nanoparticles of metal oxides on sodium silicate
micelles.
• Partial dissociation of metal oxide nanoparticles in the sodium silicate
environment as a result of acid–base influences between oxides, binder, and
solvent (alcohol).
• Hardening of sodium silicate due to the formation of hydrogen bonds and
carbonization.
The effect of the binder modification by nanoparticles of metal oxides in
organic solvents was the molding sand tensile strength Rmu increase by app.
26% (nanoparticles of ZnO in propanol) [49].
(b) At an increased temperature (at the mold pouring with liquid metal), the modi-
fication mechanism of sodium silicate influencing the improvement of knock-
ing out process contains the following stages:
• Destruction of oxide bridges between silicate tetrahedrite SiO44− in a
liquid state
• Thermal dissociation of metal oxides
• Metal cations (Zn2+, Al3+, Mg2+) building-in into the silicate lattice with
formation of bonds of the type: Si−O−Zn − O−Si; Si−O−Al − O−Si; Si−
O−Mg − O − Si [49].
Results of semi-industrial tests, presented in Fig. 9.17, confirm that the sodium
silicate modification by nanoparticles of metal oxides in various alcohols improves
the molding sand knocking out index. The best effect, expressed by the knockout
work decreased to 50%, was obtained for the system: water glass modified by MgO
nanoparticles in propanol (Fig. 9.17) [49].
Modification by Functional Nanoparticles: Zinc Ferrite
At present the newest investigations concerning the binder modification are
directed toward using multifunctional nanoparticles, which can fulfill more than
one function [58, 59]. On account of the fact that in the casting production process,
Fig. 9.17 Comparison of knocking out properties (knockout work Lw value) of molding sands
with sodium silicate modified by alcoholic solutions of nanoparticles [49]
it is very important to obtain products of the full value, the producers are striving
to optimize production conditions. One of the basic assessment criteria of the cast-
ing is the quality of its surface and microstructure of the surface layer. Effects
occurring on the metal/sand mold boundary are decisive in this case. Moreover,
processes occurring in the surface layer influence properties of the whole casting
(mechanical properties, corrosion resistance, wear resistance, etc.) [60]. Growing
customer demands for castings of metal alloys and striving to optimize their
shapes, weights, and quality as well as the environment care are forcing the casting
producers and suppliers of materials for the foundry industry to undertake research
in the field of development of new materials and alloys more environment-friendly.
Simultaneously, casting houses strive to limit the reject amount, which cause
financial losses and – in addition – the environment pollution. In the world 75% of
cast iron casting is produced in sand molds bound by various binders: organic
(synthetic resins) and inorganic (water glass, with bentonite). On account of the
environment protection [61], it is recommended in the scope of the best available
techniques to substitute molding sands with organic binders (which have a nega-
tive influence on the environment caused by emission of substances from BTEX
and PAHs groups) [62, 63] by molding sands with inorganic binders, based mainly
on sodium silicate, hardened by physical factors (drying). Sodium silicate imparts
to molding sand several characteristic properties resulting directly from the speci-
ficity of its binding mechanism, in which participate both chemical and physical
processes. As it was mentioned in the previous chapter, molding sands bound by
this binder are characterized by a small strength in the first hardening phase, since
this process does not proceed “to the end” and is again activated after the mold
pouring by liquid casting alloy. In consequence, the molding sand strength
increases at temperatures 800–900 °C, which causes problems with casting knock-
ing out from molds made of these sands. A large drawback of these sands is their
small susceptibility to the reclamation [51].
In order to eliminate or limit these defects, the modification of their sand matrix,
the modification of binders, and selection of the proper hardening way are
applied [51].
One of the most often occurring casting surface defects is a porosity. For the
majority of foundry plants, the porosity problem is causing significant losses,
since this defect decreases mechanical properties of castings. As it results from
references, the porosity effect depends on many factors, among others, on a mold-
ing sand kind, sand composition, protective coating composition, liquid metal
temperature, casting wall thickness, and additions of surface active elements (Ti,
Zr), as well as on addition of Fe2O3 into molding or core sands [64].
The results indicate that the addition of zirconium or zirconium with sele-
nium into cast iron inhibits the formation of subsurface porosity. The addition of
red ferrous oxide (Fe2O3) to cores made in the technology of sands with polyure-
tane binder, cold-bound (in amount of 0.25%), totally stopped the porosity for-
mation in castings made in sands with the participation of these cores. A
comparison of additions of Fe2O3 (red) and Fe3O4 (black) indicated a significant
advantage of Fe2O3 oxide in preventing the porosity defect in gray cast iron cast-
ings. The core protective coatings made in 100% of α-Fe2O3 as well as of the
mixture of α-Fe2O3 and water glass fully prevented the porosity formation [64].
The question arises how to explain that such small amounts of Fe2O3 are so effi-
cient in the porosity prevention. Probably, Fe2O3 oxide in a certain way influ-
ences catalytically binder decomposition products minimizing amounts of
generated gases (H2, N2). One of the theories explains this fact by suggesting
that under a sudden influence of high temperatures of the liquid foundry alloy,
red Fe2O3 oxide easily evolves oxygen. This oxygen immediately reacts with
nitrogen – formed due to the binder decomposition – forming NOx. α-Fe2O3
oxide has a higher oxide concentration in recalculating into the iron content than
Fe3O4 oxide, which can explain more efficient actions of Fe2O3 in preventing the
porosity formation [64]. In relation to the above considerations, the question
arises whether such defects as casting surface porosity, too small initial strength
of molding sands with sodium silicate at room temperature, and too high final
strength (at the knocking out stage) can be eliminated or limited by the applica-
tion of one addition to the molding sand.
Therefore the basic condition, which should be fulfilled by the modifier, is mul-
tifaceted operation. This modifier – under the temperature influence – should be
undergoing decomposition into nanoparticles of metal oxide (ZnO) and nanoparti-
cles of ferrous oxide, which will easily release oxygen. Zinc ferrite excellently ful-
fills these requirements having features of magnetic functionality and decomposing
itself into neutral for the environment and widely utilized oxides: ZnO and Fe2O3
(which at a high temperature easily gives out oxygen forming Fe3O4). The decom-
position process of zinc ferrite nanoparticles can find applications in founding or in
technologies where the active oxide is needed, e.g., water decomposition into
hydrogen and oxygen.
Detailed investigations of the possible decomposition ways of nanoscale systems
and their dependence on the cation distribution (divalent and trivalent) in tetrahedral
References 239
and octahedral places in the spinel ferrite structure are also interesting for research-
ers’ testing properties and applications of magnetic nanoparticles. Knowledge of the
decomposition process mechanism can be utilized also in the technical fields where
ferrites are applied. The good example constitutes obtaining H2 from the catalytic
decomposition of H2O (obtaining clear energy) with using zinc ferrite or manganese
ferrite as catalysts [65].
Acknowledgments This chapter was supported by the National Science Centre, Poland (Grant
Number 2016/23/D/ST8/00013).
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Chapter 10
Green Sands
10.1 General Characteristics of Green Sands
In comparing the green sand technology with chemically bound sands, two main
parameters are taken into account.
• Amount and kind of used raw materials – in the green sand, the average addition
of bentonite equals 8%. Taking into account the sand recycling, it can be assumed
that app. 7.5% of this bentonite will be used again in further cycles (assuming
that app. 0.5% of bentonite will have to be substituted by a fresh material). In the
typical technology of molding sands with chemically hardened binders, the addi-
tion of 1–3% of a binder is used, and all this amount is lost, due to a high-
temperature influence and in the reclamation process [1–3]. Such diversification
of sands is essential for the process economy.
• The second essential factor influencing the technology selection is the environ-
ment protection problem. In the case of green sands containing only bentonite
and water, only water vapor and CO2 will be evolving – in practice – into the
environment. Problems occur when organic additions are introduced to green
sands, e.g., carbon substances generating lustrous carbon.
Molding sands with bentonite, it means green sand1 is the most popular technol-
ogy of manufacturing sand molds, especially for cast iron castings. One of the rea-
sons of such wide usage of molding sands with bentonite is the possibility of using
it several times [1–3]. It can be assumed that 90% of bentonite and the selected
additions can be reclaimed and – after rebounding – used again.
The average composition of such molding sand: 85–95% of high-silica sand (but
can be also olivine or zirconium sand), 5–10% of bentonite, 2–5% of water, and – in
1
The process is called “green sand” casting not because the sand is green but because the sand is
moistened with water and clay, rather than oil. The term green sand means the presence of moisture
in molding sand indicates that the mold is not baked or dried.

244 10 Green Sands
the case of making iron castings – 3–9% of substances containing carbon, it means
substances generating lustrous carbon. These can be sea coal dust, brown coal,
products from crude oil processing, starch, wood flour, synthetic resins, plastics,
etc. Bentonite and water are acting as binders, while substances generating lustrous
carbon prevent the metal oxidation, by producing the reducing atmosphere during
the mold pouring with molten metals. They produce the lustrous carbon layer not
moistened by liquid metal, which prevents sand burn-on to the casting. Green sands
can be used for producing molds for castings of ferrous alloys, as well as of non-
ferrous metals alloys (magnesium, aluminum, copper alloys). Small, precise cast-
ings as well as large castings of a few tons can be cast.
At a uniform molding sand compaction and at maintaining a precise control of
its properties, castings of a very low dimensional tolerance are obtained. This pro-
cess is characterized by a very good efficiency, as compared with several other
processes of producing molds, and is easily mechanized.
Green sands can be hand formed, but presently the machine forming technique
with the application of automatic molding machines, shaking and pressing, press-
ing, or impulse-pressing, predominates. Especially beneficial is the flask-less for-
mation, which is highly efficient, and the produced molds are very accurate.
The green sand technology is and still will be one of the most important and the
most widely applied molding sands technology. These sands are cheap, environment-
friendly (provided that additions of substances containing carbon and generating at
high temperatures, often toxic gases and unpleasant odor, are not used), and – what
is the most important – they are reversible. This technology is efficient: applying
chemically bound molding sands, it is possible to produce 60–100 molds/hour,
while a modern foundry applying green sands is producing 600 molds/hour.
In order to meet the clients requirements, concerning the casting quality, green
sands must have the listed below features:
• High fluidity to assure the adequate compaction;
• Proper plasticity and ductility to prevent mold deformations;
• Sufficient strength to oppose the liquid metal pressure;
• High erosion resistance to prevent defects related to molding sand inclusions;
• High refractoriness to prevent molding sand burn-on on casting surfaces;
• Good knocking out ability, since it assures low cleaning costs;
• Safety for the environment (low storing costs).
Typical properties of green sands for the cast iron foundry, in dependence of the
forming method, are given in Table 10.1.
A certain drawback of these molding sands is their low plasticity, and therefore
when sand grains are not especially strongly bound, the mold – after hardening –
can be destroyed, causing scraps. Hardness limits for green sands are determined as
1.0 MPa [4]. These sands have relatively low strength in a wet state, which limits the
size of castings which can be produced in wet molds [5]. It should be noticed that
the application of worse bentonite grades increases amounts of certain specific
defects such as porosity, nonmetallic inclusions, and scabbing.
10.2 Bentonite: Structure and Properties 245
Table 10.1 Recommended properties of green sands used in the cast iron foundry depending on
the molding technique
High pressure
Parameter Jolt/squeeze machines (DISA ect.)
Moisture 3–4% 2.5–3.2%
Green tensile strength 70–100 kPa 150–200 kPa
Compactability 45–52%; 42–50% 38–40%; 25–35%
Permeability 80–110 80–100
Active clay 5.0–5.5% 6.0–10.0%
VOC 2.5% 2.0%
Loss on ignition (950 °C) 7.0–7.5% 6.0%
Table 10.2 Properties of green sands applied in various parts of the world
Parameter China India Australia Europe USA
Compactability (%) 34–36 35–39 34–36 35–37 36–38
Active clay (%) 9.0–1.0 10.0–11.0 8.5–9.5 9.0–10.0 7.5–8.5
VOC (%) 2.5–2.7 3.0–3.3 1.3–1.5 1.8–2.0 1.5–1.7
Loss on ignition (%) 4.2–4.6 5.0–5.5 2.8–3.0 3.4–3.8 2.8–3.1
Wet tensile strength (kPa) 3.3–3.5 1.8–2.2 2.1–2.4 3.3–4.0 2.9–3.3
Moisture (%) 3.3–3.6 3.5–3.8 3.0–3.2 2.9–3.2 2.8–3.0
Green tensile strength (MPa) 0.20–0.22 0.18–0.21 0.22–0.24 0.23–0.25 0.22–0.24
Permeability 120–140 130–150 70–80 120–130 110–130
Total clay (%) 12.0–13.0 13.0–14.5 11.0–12.0 11.5–12.5 10.0–11.0
Sand AFS 56–60 55–60 65–70 61–65 60–63
On account of diversification of initial materials, as well as the lines of green

sands processing, the modification of the applied bentonites – in order to be adjusted
to the existing conditions – is needed (Table 10.2). Due to that, bentonites are sub-
jected to modifications, and various additions are introduced into them. The benton-
ite modification is necessary to maintain its high position as a binder of molding
sands. As an example, adding of macrocrystalline graphite to bentonite causes that
molding sands with this bentonite obtain a higher strength.
10.2 Bentonite: Structure and Properties
Bentonite – sedimentary argillaceous rock, which takes on white, yellow, or other

colors. It has high absorption properties. It was formed as a decay result of volcanic
ashes and dusts deposited on the bottom of seas in the alkali environment. The name
“bentonite” occurred in the year 1898 and concerned the rock discovered near
246 10 Green Sands
Fig. 10.1 Crystal structure of montmorillonite. (Adapted from Refs. [11, 12])
Benton Fort in Wyoming, in the USA. The main component of bentonite, which
decides on its suitability for foundry processes, i.e., thermal resistance and binding
properties, is montmorillonite2 (MMT). It is generally accepted that the argillaceous
rock containing not less than 75% of montmorillonite is called bentonite, while
minerals containing 50÷75% of montmorillonite are called bentonite clays. Usually
bentonite is not occurring in a pure form. It is accompanied by other argillaceous
minerals, e.g., kaolinite and illite. Bentonite is a very complex mineral, and not
always the relation between its composition and binding properties can be scientifi-
cally explained [7].
Bentonite swells after water additions because it absorbs water molecules.
Therefore it is suitable as a binding material and can cover sand grains during the
mixing process. Montmorillonite – hydrated aluminum hydrosilicate – is a natural
mineral from the smectite group, belonging to the layered silicates class of the type
2:1. Montmorillonite is built of aluminosilicate packets, three-layer packets 2:1
(Fig. 10.1). Each packet consists of two tetrahedral layers and one octahedral layer
contained between them. The basic structural elements of a tetrahedral layer
(Fig. 10.2a) are silica-oxygen tetrahedrons (oxygen ions are in corners while silicon
cation in the middle of tetrahedron) joined with each other by corners. The basic
structural elements of an octahedral layer (Fig. 10.2b) are alumina-oxygen octahe-
drons joined with each other by edges (OH− ions are in corners while aluminum
cation in the middle). Peaks of tetrahedral layers are directed towards the middle of
a packet. Oxygen ions – common for both layers – together with hydroxide groups
2
Montmorillonite, mineral from the silica group, is counted to argillaceous minerals (group of
smectites). The name originates from the town Montmorillon in France.
Fig. 10.2 (a) A silica tetrahedron in which the central silicon ion is coordinated to four oxygen
ions (bright balls are oxygen atoms and black balls are silicon cations). (b) An alumina octahedron
in which the central aluminum ion is coordinated to six hydroxyls (black balls are hydroxyls, and
small gray balls are cations with octahedral coordination Al, Fe, Mg). (Adapted from Ref. [13])
trans-octahedral cis-octahedral
OH group
metals (Al, Mg, Fe)
oxygen
Fig. 10.3 Cis- and trans isomers in the octahedral structure of bentonite. (Adapted from Ref. [13])
are surrounding aluminum cations forming octahedrons of the octahedral layer.

Individual layers in the packet are joined by strong ion-atomic bonds. In octahedral
layers of montmorillonite, a substitution of aluminum cations by cations of a lower
valence (e.g., Ca2+, Na+) can occur. In result, there is an excess of negative charges
on the packet surface. This negative charge is balanced by cations adsorbed in the
inter-packet space. Since the electrostatic field of the packet is weak, these cations
are easily exchanged [8–10]. Cis- and trans isomers in the octahedral structure of
bentonite are shown in Fig. 10.3.
An individual montmorillonite particle has a form of a plate of a thickness of
1 nm and width and length: 200–2000 nm. In inter-packet spaces of montmorillon-
ite particles, exchangeable cations and small amounts of water occur. Distances
between packets are variable and mainly dependent on the amount of absorbed
water (Fig. 10.4).
On account of dominating – in inter-packet spaces – exchangeable Na+ or Ca2+
cations, sodium and calcium montmorillonites are differentiated. Mainly natural
calcium bentonites occur in the world. Deposits of sodium bentonites are not numer-
ous. These exchangeable cations can be replaced by organic and inorganic cations
through ion exchange reactions.
The bentonite composition can be shown by an approximate formula:
M x [ Al 4 -x Mg x ]x Si8 O20 ( OH )4

( Na,Ca ) x ( Al.,Mg )2 ( Si8O20 )( OH )4 ⋅ n H 2 O
248 10 Green Sands
Fig. 10.4 Structure of montmorillonite, 1 Å = 10−8 m. (Reprinted by permission from Ref. [14])
or in the case of sodium bentonite:
Si8 O20 ( OH )4 ⋅ n H 2 O
−
Na + 0,67  Al3,33 Mg 0,67 
0 ,67

where M means ions present in between plates, mainly Na+ and Ca2+. The chemical
composition of MMT nearly always differs from the theoretical composition,
because Si4+ ions can be partially substituted by Al3+ ions while Al3+ ions by Mg2+,
Fe2+, Zn2+, or Cu2+. The MMT composition depends also on the geographic location
of the deposit, on the deposit layer, and on initial materials. Bentonites, which were
formed of volcanic ashes, called Wyoming bentonites, contain sodium montmoril-
lonite (NaMMT), while bentonites which were formed as a result of weathering of
rocks contain usually calcium montmorillonite (CaMMT). These two kinds of ben-
tonites have very different properties. Natural calcium bentonites are not swelling
and gelling when they are mixed with water. Due to that, they are not applied in a
foundry practice. However, calcium bentonites can be activated by caustic soda, and
in result the so-called soda-activated bentonite is formed. Bentonites of this type are
widely applied in ferrous alloys foundries, and their parameters are reaching values
of natural sodium bentonites. The activation process of calcium bentonite by sodium
carbonate is presented below:
Na 2 CO3 + Ca 2+ – montmorillonite → 2 Na + – montmorillonite + CaCO3

The activated bentonite has a higher ability to absorb water and better mechani-
cal properties (Table 10.3).
Table 10.3 Properties of typical foundry bentonites used in various countries and mold sands with
these bentonites
Parameter Chine India Australia Europe USA
Cation exchange capacity (CEC) (meq/100 g) 88 96 74 84 100
Total hardness 9 16 7 14 20
Soluble CaCO3, % 4.25 3.2 1.2 3 2.6
pH 9.6 9.64 9.64 9.9 9
Free swelling, m/s 23 23 28 28 34
Mechanical impurities (%) 2.6 2.2 3 2.7 2.6
Molding sand: silica sand + 7% bentonite
Moisture, % 2.7 2.2 2.2 2.3 2.6
Compactability % 41 40 39 40 40
Permeability 160 130 167 165 145
Green tensile strength, MPa 0.13 0.19 0.127 0.169 0.141
Wet tensile strength, kPa 3.2 3.8 3.0 3.7 3.1
Natural sodium bentonites are significantly swelling during mixing with water.
Their main features in green sands are high strength, high tolerance for differences
in water content, high resistance to overheating, as well as a durability at high tem-
peratures. One of the basic features of montmorillonite is its ability to absorb ions
from aqueous solutions (the so-called ionic capacity) and the cation exchange
capacity (CEC). The ionic capacity is determined in milliequivalents of the given
ion for 100 g of bentonite (meq/100 g). The swelling ability manifests by water and
other polar liquid penetrations in between layers, causing changes in lattice dis-
tances. As the laboratory tests indicated, the volume increase, when sodium mont-
morillonite was mixed with water, could reach even 1400–2000% (it can absorb 5
times more water than it weights), while for calcium montmorillonite, this increase
equalled 45–145%. The CEC coefficient for montmorillonite is within the range
from 80 to 150 meq/100 g [15]. Sodium montmorillonite is also characterized by a
large specific surface: 700–800 m2/g.
Following factors influence the swelling process of sodium bentonite:
• Polarization of water molecules
• Geometrical affinity of a water layer with tetrahedral layer of the packet
• Negative charge on the packet surface
• Sodium ion presence in exchangeable positions
Not swelling lattices have the same structure as lattices which are swelling, but
they differ by the kind of atoms present in a matrix.
Molten metal pouring into a mold made of green sand causes a moisture removal
from a molding sand and a partial destruction of montmorillonite structure (together
with a destruction of additions, if they were in sand). In this part of a mold, in which
a molding sand did not reach the deactivation temperature of bentonite, there is still
active montmorillonite able for swelling.
250 10 Green Sands
When bentonite poured with molten metal and then cooled remains below the
deactivation temperature, its laminated structure together with the swelling ability
is maintained. The deactivation temperature is different for different types of ben-
tonites [16–18].
Two kinds of water occur in montmorillonite:
• Bound water (occurs in a lattice), which starts evaporating from a temperature of
100 °C (when there is too much of this water, the devices of mechanical transpor-
tation can become blocked, when too small it would be difficult to water benton-
ite again);
• Structural water, occurring in the montmorillonite plate structure (responsible
for durability of bentonite – evaporates at app. 500 °C), when bentonite losses
this water, its structure disintegrates, and bentonite losses its bonding
properties.
The following processes can occur in montmorillonite, under the temperature
influence:
• Dehydration (from room temperature – 300 °C);
• Dehydroxylation (650–700 °C or 500–550 °C);
• Transformation of a crystalline structure into an amorphous form (maximum
at 900 °C);
• Disintegration and recrystallisation (return to a crystalline structure)
(850–950 °C).
The temperature range of each of these transformations depends on the chemical
composition of montmorillonite. Thus, at a higher iron content, the dehydration
process occurs at a lower temperature. Two first processes are endothermic and are
accompanied by a molding sand weight loss. The third process – however also
endothermic – occurs without the weight loss. During the dehydration process,
water adsorbed on the outer surface and inter-packet water are desorbing in endo-
thermic reactions within the range: from room temperature to 300 °C [19, 20].
Montmorillonites, which undergo dehydroxylation at a temperature of 700 °C,
are called “normal” or ideal, while these which undergo dehydroxylation at a tem-
perature of 500 °C are called “abnormal.” According to Stoch [21], montmorillonites
of volcanic origin belong to the first group while montmorillonites being the effect
of rocks weathering to the second group.
During dehydroxylation a water molecule, formed of two hydroxylic groups,
migrates outside a mineral:
2 ( OH ) → H 2 O + O r. ( r  residual,remains in the structure )

High-quality bentonites indicate higher temperatures of dehydroxylation.
Bentonites containing contaminations (e.g., iron) have worse resistance to the dehy-
droxylation process [22, 23].
10.3 Additions Generating Lustrous Carbon 251
Characteristics of sodium and calcium bentonite are completely different.

Sodium bentonite as compared with calcium bentonite has a higher expanding abil-
ity, higher bonding ability, better thermal stability, and higher resistance to an
increased temperature influence.
Bentonites intended for foundry practice should fulfill the following technologi-
cal requirements [24]:
• High bonding ability to guarantee obtaining molds of an adequate strength
• High thermal stability to decrease bentonite consumption at a molding sand
rebounding
• High reclaimability, possibility of water readsorption to obtain proper bonding
properties
• High compression strength to limit the defects number
• Fast obtaining of properties during mixing, even when conditions are not optimal
(e.g., increased temperature of a molding sand)
Several modification methods of bentonites were worked out, concerning
improvements of their properties and thus improvements of molding sands. These
works are mainly aimed at decreasing the water demand. The most often applied,
but not the only, modifiers of bentonite are graphite, zeolite, and lignite (brown coal
variety). One of the modification methods (Quickbond process patented by S&B
Industrial Minerals) applies additions of microcrystalline graphite, which impreg-
nates bentonite surfaces during mixing, and improves mechanical properties since it
increases the montmorillonite surface which allows for a faster water adsorption. A
lower water demand and lubricating effect of graphite reduce friction between
matrix grains, due to which the adequately high fluidity of molding sands is obtained
and less energy is needed for pressing molding sand grains, which leads to more
uniform compaction of the mold surface, especially in places with a difficult access.
A better compaction and higher mold density reduce the pores’ volume, decrease
permeability, and limit risks of molding sand erosion, because the surface of bond-
ing bridges in bentonite is increasing, and the contact between aggregates of grains
becomes better. Dimensional inaccuracies of castings are smaller, and the manufac-
tured castings are of a lower coarseness. As an example of an advantageous influ-
ence of the crystalline graphite addition, the improvement of molding sand fluidity
can be used [23].
10.3 Additions Generating Lustrous Carbon
At manufacturing castings of cast iron, it is necessary to introduce into green sands

lustrous carbon formers (LCF), which are able to generate “lustrous carbon” (LC).
Its purpose is maintaining a reducing atmosphere in a mold and to prevent defects
related to oxidation, which reason is moisture content. This is not a graphite but a
carbon variety similar to carbon black [4]. For the given molding sand compactibil-
ity and coarseness of its matrix, the water demand is determined by the bentonite
252 10 Green Sands
fraction. It means that when the bentonite addition is increased, the LCF addition
should be also increased to eliminate the oxidation inside the mold cavity. The most
often used additions generating lustrous carbon are sea coal dust, brown coal dust,
pith, and asphalt.
Coal dust
• Sea coal dust is – from 50 years – the traditional LCF addition. This dust is usu-
ally added to green sands used for making molds poured with cast iron. It is also
used, but to a limited range, for making castings of non-ferrous metals. Small
amounts of sea coal dust can be mixed with resins and oils. This addition is ther-
mally degraded during casting and due to that lustrous carbon, which improves
the casting surface quality and knocking out ability, is formed. There are three
reasons of adding sea coal dusts to molding sands [25, 26].
• Gases liberated during a mold heating or during pyrolysis of sea coal dusts are
creating at the initial stage the neutral atmosphere in the mold cavity while in the
later period the reducing atmosphere, which limits reactions between liquid
metal and a mold material.
• Ability of forming – on high-silica grains – thin layers of lustrous carbon not
wetted by liquid cast iron, due to which the wettability of mold surfaces is
decreased and the liquid metal penetration inside a mold is limited. Owing to this
fact, a wettability of the mold surface decreases, limiting the liquid metal pene-
tration into a mold, which reduces works needed for cleaning of castings as well
as prevents the defect formations.
• During the thermal decomposition of sea coal dusts, a coking material is formed,
which after heating indicates a certain elasticity, forming something like a “pil-
low” in between matrix grains, and thus reduces the compressive stress inside a
mold and mold wall movements. At the same temperature range as transforma-
tion, α quartz → β quartz (573 °C) [27].
According to Richardson [30] and Engelhard [14, 26], after pouring with molten
metal the green sand with carbon-containing additives, the following pro-
cesses occur3:
• An oxidizing atmosphere is created in the mold cavity (Fig. 10.5). At a tempera-
ture above 200 °C, water vapor and aliphatic hydrocarbons start liberating them-
selves from sea coal dusts. The pyrolysis of carbon, contained in dusts, occurs,
3
Natural fuels are utilized in thermochemical transformation processes, to which belong:
• Burning – thermochemical process performed in the oxygen presence; the basic prod-
ucts of the process are CO2 and H2O.
• Gassing – process of total thermochemical transformation performed in the presence of
oxygen or air with water vapor addition; a mixture of combustible gases, first of all, CO, H2, and
hydrocarbons, as a potential fuel with a simultaneous decomposition of water vapor into oxygen
and hydrogen, are formed. High oxygen concentration is created in the mold cavity.
• Pyrolysis – thermochemical process performed without the oxygen access, in the result
of which solid, liquid, and gaseous products are formed.
• Liquefaction – process aimed at producing liquid fuels out of natural solid fuels.
a) b)
Reducing Precipitation
Mold
atmosphere of lustrous carbon
atmosphere N2 O2
Softening of
coal to from cocke
Melt Gas phase
Fig. 10.5 (a) Oxidation atmosphere in the mold cavity before pouring with molten metal. (b)
Emission of lustrous carbon from gaseous phase on cooler surfaces. (Reprinted by permission
from Ref. [14])
Pyrolysis Dehydration Condensation

Sea
CH4 CH CH
coal 300 - 500 °C 800 - 1200 °C 800 - 1200 °C
Fig. 10.6 Formation of benzene from sea coal dust (pyrolysis, dehydration, and condensation).
(Adapted from Ref. [28])
Fig. 10.7 Reactions in CH4 + 2O2 → CO2 + 2H2O

result of which the CO2 + C → 2CO
reducing atmosphere is C + H2O → CO + H2
formed in a mold
and aromatic hydrocarbons of low boiling points (from the BTEX group) start
emitting (Fig. 10.5a). These hydrocarbons are emitting in a gaseous form during
pouring, cooling, and molds knocking out. Hydrocarbons and carbon, from a
metal bath or from carbon carrying substances, are reacting with oxygen. Gases
generated in these processes are pushing away from the mold cavity (via vents,
riser heads, or by diffusing through the upper half of the mold) gases – which
were initially present there – and the reducing atmosphere is forming (H2 and
CO). Such atmosphere prevents – to a significant degree – oxidation reactions
(Fig. 10.5b) [14] (Figs. 10.6 and 10.7) [28].
The formed benzene is then forming naphthalene, which is subjected to succes-
sive reactions forming polycyclic aromatic hydrocarbons of high boiling points [29].
Substances from the BTEX group are emitting to the atmosphere while from the
PAH group, on account of their very small pressure, are absorbed by molding sands
and then constitute a problem during storing of spent molding sands. As investiga-
tions indicate [28], substances from the BTEX group are formed from sea coal
dusts, in large amounts only when the temperature is above 600 °C.
254 10 Green Sands
• At temperatures of 550–600 °C, carbon starts softening and becomes plastic,

simultaneously increasing its volume as a result of swelling. The carbon swelling
effect occurs at the same temperature as the transformation of quartz sand
(T = 573 °C) and increase of its volume (α-quartz → β-quartz).
• At temperatures of 650–900 °C, lustrous carbon from gaseous volatile hydrocar-
bons is deposited on cooler mold surfaces.
However, it should be noticed that both the excess and deficiency of lustrous
carbon can negatively influence the casting quality. A deficiency of lustrous carbon
in green sands can be causing casting defects such as burn-on or penetrations of
liquid metal into a mold. An excess of lustrous carbon in a molding sand, especially
when it is together with a core sand originated from burned cores made in the cold-
box technology with using amines, can be the reason of a defect called “elephant
skin” [30]. At large amounts of lustrous carbon, its layers can separate themselves
from the mold surface and be caught by liquid metal forming there such skin.
Another negative side of too high amounts of sea coal dusts in a molding sand is
the fact that the water demand of this sand increases since the amount of a light
porous material such as coke, being the hydrolysis product, increases.
In the case of producing spheroidal cast iron, the range of inclusions of magne-
sium oxide (MgO), often visible as pinholes, can be reduced when the amount of
carbon in a molding sand is sufficient to prevent the reaction between residual Mg
from a bath and oxygen from the mold atmosphere. These oxide inclusions are usu-
ally seen as stringers, and they negatively influence the casting quality and its
mechanical properties.
However, when sea coal dusts are not present in a molding sand, as a result of the
moisture gasification, the atmosphere in the mold saturates with oxygen and hydro-
gen producing a highly oxidizing environment favoring a surface ferrous oxidation
to FeO, which in turn reacts with SiO2 forming liquid slag Fe2SiO4, called fayalite.
This slag easily penetrates into the mold surface and after solidification forms burn-
on sand. In such case, it is necessary to apply protective coatings to avoid a liquid
metal penetration. The presence of additions containing carbon in green sands pre-
vents this effect occurrence.
Substitutes of Sea Coal Dusts
As far as green sands are environment-friendly, an introduction to them of sea coal
dusts as a lustrous carbon source makes these sands very harmful for employees and
for the environment. The reason of this effect is mainly the harmfulness of products
of coal dust thermal decomposition (emissions of PAHs and substances from the
BTEX group). The highest concentrations of HAP were found for benzene, toluene,
xylenes, ethylbenzene, and naphthalene, which – in approximation – constituted
87% of all emitted substances. Other substances formed when molds with bentonite
are poured with liquid metal are phenol, dimethylphenol, trimethylbenzene, propyl-
benzene, methylnaphthalene, dimethylnaphthalene, ethyltoluene, and cresol [31]. A
comparison of emissions from a green sand and from this sand with additions of
coal dusts indicated that the emission of HAPs was in the second case 13 times
higher [32, 33].
Also technological reasons are limiting the application of coal dusts, e.g., the
sulfur presence in the case of producing castings of spheroidal cast iron or a signifi-
cantly higher ability to generate lustrous carbon (the lustrous carbon generation
should be on the level of 7–11%). In the case of castings of spheroidal or vermicular
cast iron, the sulfur content in the substance forming lustrous carbon should not
exceed 1%. At its higher concentration, an accumulation of sulfur in a molding sand
can occur. When a sulfur content exceeds 0.1%, sulfur reacts with magnesium,
inhibiting formation of a spheroidal structure in cast iron. Therefore activities of
bentonite producers are focused on the selection of such substances forming lus-
trous carbon which would provide the same favorable technological effect as sea
coal dusts (forming reducing atmosphere during pouring with liquid metal and min-
imizing casting defects), being at the same time less harmful for the environment.
In order to limit harmful influencing of green sands and to assure the optimal
quality of bentonite, more and more often the especially prepared ready mixtures of
bentonite with substances generating lustrous carbon are supplied to foundries.
Most often the mixtures, in which only a part of coal dusts is substituted by another
mineral having the ability of forming lustrous carbon, are applied [23, 34].
In cast steel casting, coal dusts are not used, since carbon is entering into alloys,
whereas starch additions are used for molding sands destined for making steel cast-
ing. Starch additions are introduced into fresh molding sands in amounts of
0.50–0.75%. Since a part of this amount undergoes the thermal decomposition dur-
ing pouring, it is recommended to introduce additionally 0.10–0.25% of starch after
each pouring cycle [35]. Starch prevents casting defects related to swelling, since it
makes possible the sand deformation without the mold deformation at burning.
Starch is a material of an alkaline reaction. Dextrin is a product of the second starch
polymerization, formed by subjecting starch to the influence of acids and high tem-
peratures. Dextrin improves a fluidity and favors maintaining moisture and prevents
drying and brittleness of mold edges.
However, addition of this substance does not improve a mold resistance to the
erosion and to the metal penetration into a mold [6, 36, 37]. Characteristics of the
most often applied substitutes of sea coal dusts, generating lustrous carbon, are
Usually these materials are less harmful for the natural environment than coal
dusts; they cause smaller amounts of fumes during casting, but some materials sub-
stituting coal dusts are generating larger amounts of PAHs [6, 33].
Mixtures of Bentonite + Substance Generating Lustrous Carbon
Companies, bentonite producers for foundry practice, started in recent years pro-
ducing mixtures of bentonite with substances forming lustrous carbon. These mix-
tures are the most often individually prepared for the given foundry, in dependence
of the applied cast iron grades and kinds of produced castings. Such mixtures have
several advantages:
• They are easy in using, since their composition is selected for the given foundry.
• They are safe; there is a small risk of self-ignition of such mixture.
256 10 Green Sands
Table 10.4 Substitutes of sea coal dusts

Content of volatile Lustrous Loss on Release temperature of
compounds (%) carbon (%) ignition (%) volatile compounds (°C)
Sea coal 34–40 13.8 93.4 400–500
Anthracite 3–6 1–3 90–95
Coking coal 2–4 <1 90–95
Petroleum coke 2–3 <1 95–99
Graphite <1 <1 85–99
Lignite 45–65 5–8 90–94
Natural resin 85 43.8 99.9 300–400
Synthetic 94 56.2 99.9 250–350
hydrocarbon resin
• There is a smaller consumption of a mixture as compared to traditional two com-

ponents introduced into a mixer.
• Water consumption by a molding sand is decreased.
• Casting surface quality is significantly improved.
Mechanism of the Lustrous Carbon Formation

P. Jelinek et al. [38] investigating the thermal destruction processes of carbon and its
mixtures with additions containing carbon found that the pyrolysis process of these
substances in molding sands occurs in two stages, according to the scheme below.
In places where a molding sand reaches a temperature of app. 900 °C
Stage 1 (primary pyrolysis):
o
coal + C-additives 5
900 C
o → semi　 coke + tar + water1 + gas1
C /min,

when a molding sand temperature increases to 1100 °C
Stage 2 (secondary pyrolysis):
o
tar + water1 + gas1 1100

 C,
→ PC + water2 + gas2
Pyrolytic carbon (PC) consists of two, morphologically different forms: amor-

phous carbon (AC) and lustrous carbon (LC) and of fugacity carbon (semi-coke) FC:
PC = AC + LC + FC
gas1 – mixture of aromatic and aliphatic hydrocarbons

gas2 – mixture of simple gases, difficult to be decomposed (CO2, CO, H2, CH4, etc.).
These three forms of solid carbon, AC, LC, and FC, being pyrolysis products, are
having various properties.
10.4 Water and its Role in Green Sands 257
Amorphous carbon (AC) is a properly out-gassed carbon containing 97–98% of

C and 0.5–0.7% of H2. It has a typically spheroidal form of “grapes clusters.”
Density of 1.89–1.95 g cm−3, average aromatic properties 0.072, and oxidizability
(thermogravimetrically measured) app. at 630 °C. Amorphous carbon is the main
component of pyrolytic carbon (PC). It is formed as a result of the homogeneous
nucleation directly from the gaseous phase. On account of its physical and chemical
properties, it is close to black carbon.
Lustrous carbon (LC) forms a very compact film of immeasurable volumes of
pores. This is a highly out-gassed smaller part of pyrolytic carbon (PC) (0.23–0.37%
H2), with the average aromatic properties 0.037 and the smallest oxidability at app.
807 °C. Out of all substances containing carbon, it is characterized by the highest
compaction degree (density 2.08–2.13 g cm−3). On account of a similarity of its
crystallographic lattice to quartz, LC is formed as a result of heterogenic nucleation
at a high adhesion to quartz sand. It is deposited from the gas phase on hot surfaces
in the temperature range of 650–1000 °C. It is formed on the metal bath surface on
the approaching liquid metal front. On account of its hexagonal lattice, it is similar
to graphite.
Semi-coke represents the largest part of carbon formed in the pyrolysis process
of bentonite mixtures containing additions with carbon.
Ferrous Oxide
Ferrous oxide reacts with quartz at high temperatures forming low-melting compo-
nent, fayalite. This glassy, plastic product causes sintering of grains.
Ferrous oxide is mainly applied at the core production in order to limit the veins
formation [39].
10.4 Water and its Role in Green Sands
Water is an indispensable component of green sands. Its addition depends on the

quality and amount of bentonite and on the molding sand destination (for wet or dry
molds). In molding sands intended for wet molds, the water–clay ratio (weight ratio
of water to bentonite) usually equals from 0.35 to 0.50. However, in molding sands
intended for forming under high pressure, this water–clay ratio can be lower. A
water content in molding sands destined for dried molds is higher and equals from
0.5 to 0.7.
Water applied for green sands should be clean and of neutral or basic pH (acidic
pH makes bentonite swelling difficult). pH value of water and sand should be regu-
larly controlled. When it drops from 8.0 to 6.0, more bentonite should be added to
obtain the proper strength. This problem can be solved by modifications of a mold-
ing sand pH. Water can contain such components (in a form of electrolytes), which
will be unfavorable influencing bonding properties by deactivation of bentonite.
Especially dangerous are F− and Cl− ions which, due to multiple circulations of a
molding sand, can cumulate in it. Strange electrolytes are causing the tensile
strength decrease in the condensation zone [5, 40–42] (Fig. 10.8).
258 10 Green Sands
Fig. 10.8 Influence of salt (NaCl) on the bentonite activity. Salt deactivates electrostatic bonds of
bentonite. (Reprinted by permission from Ref. [14])
Deactivation of Bentonite
This part of bentonite, which was heated to a temperature above 500 °C, losses its
structural water and thus its bonding properties and is depositing on grain surfaces.
Therefore at rebounding, apart from water and fresh sand, a certain amount of active
bentonite (mixture) is added.
10.5 Thermophysical Properties of Green Sands
Thermophysical properties of molding sands have the essential meaning for the heat
exchange between a casting and a mold. This is very important in the case of solidi-
fication and cooling of castings, when the heat abstraction rate influences the struc-
ture and properties of castings. Molding sands containing water indicate special
thermophysical properties, forming the so-called condensation zone. A low thermal
conductivity coefficient of molding sands causes that only their external layers are
heated in the mold cavity, while more deeply situated layers are of much lower
temperature. After pouring of liquid casting alloy into a mold made of green sands,
the heat of hot metal (of a temperature highly exceeding the water boiling point),
will rapidly heat the mold surface causing evaporation of water and other solvents
from a thin molding sand layer. A part of vapor can leave a mold cavity together
with the air through flow-off or risers. The remaining vapor is relocating deep into
10.5 Thermophysical Properties of Green Sands 259
Fig. 10.9 Structure of the heated surface of a green sand mold, against a steel casting, and the
forms of silica (after Sosman R.R. 1927) with solid lines denoting stable states and broken lines
denoting unstable states. (Reprinted by permission from Ref. [4])
the mold where it condenses on cold sand grains and the condensation zone is
formed. In the case of green sands, the condensation zone has significantly lower
strength and permeability than the remaining part of a mold. The condensation zone
constitutes one of the essential factors favoring surface defects of castings, such as
buckles and veins. This zone is shifting deep into a molding sand as far as it is
heated by liquid metal. This is a continuous process – dry and wet zones are moving
through a mold.
Four zones can be distinguished in molding sands with bentonite, as it is marked
in Fig. 10.9 [4]:
1. Dry zone, in which a temperature is high (above 100 °C) and all moisture evapo-
rated from a binder. The atmosphere in this zone is all the time – in practice – the
same, consisting in 100% of water vapor. Very dry vapor will react with the cast-
ing surface forming oxide and free hydrogen.
2. Vapor transportation zone of a constant temperature of 100 °C and of nearly
constant water content. As far as heat from solidifying casting is diffusing deep
into a mold, this zone is also shifting deeper into a mold.
260 10 Green Sands
3. Condensation zone, in which water vapor condenses on cold grains of a molding

sand matrix. A growing water content causes that this zone has a lower strength
than initial molding sand, and therefore mechanical defects are the most proba-
ble to occur in this zone. This zone constitutes also one of the essential factors
favoring a formation of casting surface defects (veins, buckles).
4. External zone, in which a temperature and water content are the same as in the
initial mold.
10.6 Rebounding and Reclamation of Green Sands
A scheme of arrangement of devices in typical foundry using green sands is shown

in Fig. 10.10.
Until not long ago, green sands were only subjected to a rebounding process.
Such process can be performed several times. A circulating sand is usually cooled
(e.g., in fluidized coolers) before rebounding, to prevent moisture losses and con-
densations on patterns and cores. Simultaneously circulating sands are dedusted. It
is necessary to remove metal parts from circulating sands. This is realized by means
of magnetic separators and not active bentonite, coal dusts, and ashes. Crushing of
molding sand aggregates is advantageous; however it must be done without crush-
ing of sand grains.
The final stage of the molding sand preparation for rebounding is its sieving to
remove remains of aggregates [17, 43].
The rebounding process contains supplementing of water and adding fresh ben-
tonite to substitute this part of bentonite, which underwent deactivation due to high
temperatures. Usually, supplementing of molding sands by adding fresh sands (e.g.,
spent core sand with organic binders) is also necessary.
The following amounts of additions are usually applied, at a molding sand
rebounding [6]:
• 0.3–0.5% of fresh bentonite
• 0.3–0.5% of coal dust (or 0.2% of dextrin in the case of cast steel castings)
• 1.5–2.5% of water
In addition, fresh high-silica sand (up to 10%) should be added in amounts
dependent on a core fraction in a mold. Cores with phenolic–polyisocyanate binder,
which can worsen molding sand properties, should not be used [44].
The molding sand after rebounding should have parameters very similar to
parameters of a fresh molding sand. The foundry is left with a dilemma whether to
rebound a molding sand with a high-quality bentonite (of a large montmorillonite
content) or with a low-quality bentonite (of a low montmorillonite content), but
then – in order to obtain the required properties – the bentonite consumption will be
2–3 times higher. Besides, not always using large amounts of worse quality benton-
ite, the required parameters can be obtained. In addition, the application of worse
10.6 Rebounding and Reclamation of Green Sands 261
Fig. 10.10 Schematic presentation of distribution of devices in the foundry using green sands.
(Reprinted by permission from Refs. [16, 43])
262 10 Green Sands
bentonite grades leads often to an increase of such defects as porosity, nonmetallic

inclusions, scrubbings, and water explosion [23].
When cores are used, their strength must be higher than the strength of the mold
produced of green sands, and simultaneously they should be easily knocked out
after cooling a casting. Therefore cores for green sands are usually made of molding
sands with chemically bound binders. The knocked out molding sand contains par-
tially burned out bentonite and a relatively pure molding sand (with a small amount
of a binder) made of burned out cores. This spent core sand can be treated as an
element of sand rebounding, instead of fresh sand. In such case, the kind of a binder
applied for a core sand (e.g., its chemical character), as well as the core fraction in
a mold, is important.
As indicated investigations of Śpirutov et al. [45], the compressive strength of
green sands was increasing after the introduction of a burned core sand from the
cold-box technology, while introductions of molding sands originated from the
Croning’s technology or molding sands with phenol-formaldehyde resol type resin
(hardened by CO2) were causing a decrease of strength properties of green sands.
After the casting knocking out a large part of sand originated from burned out
cores is supplied to a mixer. This sand character, which is changing during the pro-
cess of manufacturing a casting, depends on several factors, e.g., ratio of metal-
molding sand, casting size, liquid cast iron temperature, and time of a casting being
in a mold. It is, among others, a result of the fact that some binders during their
thermal decomposition in a mold – where it is a reducing atmosphere – are deposit-
ing on grain surfaces in a form of a carbon film. In order to determine how much of
a core sand should be added to a green sand, it is necessary to perform certain cal-
culations on the bases of measuring the active bentonite content and ignition
losses [46].
The amount of bentonite added to rebound a molding sand depends on its proper-
ties (binding ability, high-temperature resistance) and on conditions in a mold (cast-
ing alloy temperature, ratio of a molding sand weight to casting weight, casting
weight, time of casting being in a mold). Generally it means that the amount of
bentonite necessary for a molding sand rebounding is equal to the amount of ben-
tonite which lost its bonding properties. The higher pouring temperature, larger and
thicker casting walls, and higher ratio of metal amount to molding sand amount in a
mold, the higher will be the decomposition degree of bentonite of substances gen-
erating lustrous carbon and of other additions.
Grefhorst [37] investigated the influence of the addition of sands of burned out
cores hardened by water glass on the properties of green sands. Substitution of 25%
of fresh sand by a core sand nearly did not have any influence on properties of green
sands. Only the wet tensile strength decreased from 0.30 Pa to 0.23–0.26 Pa. When
all fresh sand was substituted by a core sand, properties of a molding sand were
significantly worse. The green tensile strength dropped to 0.10–0.18 Pa, and the wet
tensile strength dropped abruptly from 0.39 MPa to even 0.18 MPa.
The mixing process of green sands is very important, since apart from a homog-
enization of a molding sand composition, the formation of good adhesive joins of
the bentonite and water mixture with surfaces of grains of sand matrices is neces-
Fig. 10.11 Bridge between sand grains in green sands. (Reprinted by permission from Ref. [14])
sary. For this aim edge runner mixers are used. They realize two processes: grinding
and kneading. Presently rotor mixers (turbine) are widely used. The mixing time is
also very important. Too short mixing causes that bonding properties of bentonite–
water mixture are not fully utilized (Fig. 10.11).
Classic molding sands are also subjected to maturing and aeration operations.
These operations are advantageous because a molding sand taken out from a mixer
is often caked, and it would be difficult without aeration to obtain a smooth surface
of a mold cavity and thus of a casting. Water added to a molding sand during a short
mixing time is not able to create the optimal system of the bentonite–water–sand
matrix. Therefore, in order to unify molding sand properties, it is justified to leave
it for maturing for at least 2 hours after pouring out from a mixer. The strength and
permeability of a molding sand in a wet state as well as its plasticity are increasing [5].
On account of the fact that the composition of the rebounded molding sand is not
exactly known, performing systematic tests of circulating molding sands is neces-
sary. Testing should contain the following parameters (the most important are
underlined) [5]:
• Water content
• Tensile strength in a moisture state
• Compactibility
• Permeability
• Loss on ignition
• Volatile parts content
• Tensile strength in a wet state (in the condensation zone)
• Amount of active bentonite
• Compression strength in a wet state
Reclamation of Molding Sands with Bentonite
On account of growing prices of raw materials, transport, and storage costs of
wastes as well as requirements concerning the environment protection, especially
the waste management, green sands should be also subjected to the reclamation
264 10 Green Sands
process, not only to the rebounding process. The processing technology of slugs
from wet dedusting of green sands, developed by the S&B Industrial Minerals
Company, allows to recover bentonite, substances containing carbon and fine silica
[37]. The recovered molding sand components are used for preparing the new sus-
pension, which is introduced directly into the mixer. This suspension usually con-
tains 70–80% of bentonite and 20–30% of organic substances. The recovered fine
silica contains small amounts of bentonite (3 to 7%) and organic substances (1 to
4%) and thus can be successfully reused for molding sands rebounding. Molding
sands prepared with the addition of recovered bentonite indicate better compact-
ibility and strength. Especially valuable are dusts from dry dedusting of the station
for green sands processing, because they still contain significant amounts of active
bentonite and carbon. Therefore they can be still processed to recover these
components.
Ecological Technology of Preparing Molding Sands Under Vacuum Condition
Return green sand should have a temperature below 40 °C. In the case of foundries
of limited possibilities of expanding, this condition is often difficult to be fulfilled.
However, this is not the only condition to achieve the proper covering of sand grains
with a binder, in the case of green sands. These sands require the proper refinement
and aeration.
These tasks can be realized in one device, the so-called vacuum mixer, where a
dependence of the boiling point of the given liquid on the pressure in the system is
utilized. As an example, if the outside pressure is lowered to 0.01 MPa, water starts
boiling already at 40 °C (Fig. 10.12). Water evaporation is related to the cooling
effect. The transformation of liquid water into vapor absorbs energy of 2257 kJ/kg.
Processes of mixing, cooling, and preparation of molding sands occur simultane-
ously in the vacuum mixer. The scheme of such installation is shown in Fig. 10.13.
After loading the return molding sand to the mixer-cooler, two portions of water,
equal in practice, are added:
• Water necessary to wet a molding sand to provide its final wetness. This amount
of water remains in a molding sand.
Fig. 10.12 Dependence of 1000

the water boiling
temperature on the outside 800
Pressure, x102 Pa
pressure
600
400
200
0
0 20 40 60 80 100
Temperature, °C
Fig. 10.13 Molding sand preparation plant with vacuum mixer-cooler. (Reprinted by permission
from Refs. [16, 47])
• Water introduced additionally to a molding sand, necessary for cooling this sand
to the required temperature. This water is condensed and reused.
The application of vapor at the lack of air leads to a fast activation of bentonite,
due to which the bonded molding sand achieves very fast its optimal compression
strength and also:
• Its green strength increases, on average by 13%.
• Tensile strength in the condensation zone increases, on average by 19%.
• Permeability increases by 18%.
These properties are decreasing after 72 hours, but they can be restored by
90 seconds of remixing.
The application of a vacuum mixer reduces by half the emission of dusts,
decreases bentonite consumption, and contributes to energy saving.
The application of vapor at the lack of air leads to a fast activation of bentonite,
due to which the bound molding sand achieves very fast its optimal compression
strength and also:
• Its green strength increases, on average by 13%.
• Its tensile strength in the condensation zone increases, on average by 19%.
• Its permeability increases by 18%.
266 10 Green Sands
These properties are decreasing after 72 hours, but they can be restored by
90 seconds of remixing.
The application of a vacuum mixer reduces by half the emission of dusts,
decreases bentonite consumption, and contributes to energy saving.
Green Sand and Additions of α-Starch
Starch is a polysaccharide composed of two kinds of polymer chains: amylase
(20–25%) and amylopectin (75–80%). Starch is most often obtained from corn or
potatoes. Raw starch cannot be used as a binder of molding and core sands, on
account of too low strength both in solid and liquid states as well as a small resistance
to moisture. Natural starch absorbs large amounts of water during swelling.
However, only starch subjected to a modification process obtains adequate proper-
ties, due to which it can constitute a valuable binder component [48]. Nevertheless,
from many years, starch dissolved in water has been applied as an addition to green
sands, in order to increase the molding sand strength before hardening or drying
(drying temperature: 160–180 °C). The proper starch addition into green sands pre-
vents casting defects related to swelling of quartz grains of the matrix. During a
mold pouring, starch is gasified, due to which empty spaces are formed between
grains and they eliminate the swelling of matrix quartz grains. The presence of
starch in these sands can decrease a molding sand fluidity as well as a resistance to
liquid metal penetration deep into a mold [49]. The authors found that the dry com-
pression strength of green sands with starch increases when modified starch is
added, while it decreases when bentonite addition increases. However, the dry ten-
sile strength of molding sand with modified starch increases with the bentonite
addition. In order to obtain the proper wet tensile strength value, the water content
should be equal 3.5–4.5%.
Investigations concerning gas emissivity indicated that molding sands with mod-
ified starch and bentonite generate twice less gases than molding sands with other
organic binders (oil molding sands, molding sands with furan resin) while app. 50%
more than molding sands with water glass.
The developed cores with bentonite and modified potato starch were successfully
applied for making steel castings, iron castings, and aluminum alloy castings.
Green Sand and Additions of Dextrin
Dextrin is a product of not total decomposition of starch. It is obtained as a result of
a thermal processing of natural starch. The so-called yellow dextrin, which is nearly
completely soluble in water, found its application in a foundry practice. It is bond-
ing by dehydration – the molding sand drying temperature equals 160–180 °C. Dextrin
is added to green sands in order to decrease sand friability, while it is added to mold-
ing sands with other binders in order to increase their strength before hardening or
drying. It is also used as a bond stabilizing material for protective coatings. The
dextrin addition to core sands limits the possibility of occurrence of casting defects
such as buckles or veins [5, 50].
10.7 Limitations of Negative Influences of Green Sands on the Environment and Work… 267
10.7 L
imitations of Negative Influences of Green Sands
on the Environment and Work Conditions
Generation and Emission of Harmful Gases

As far as green sands without additions containing carbon are fully safe, the addi-
tion of coal dusts causes that such sands are ranked as highly harmful sands for the
environment and people. The reason of this constitutes the emission of several dan-
gerous gases from the BTEX and PAH group generated under an influence of high
temperatures of liquid metal. The results of dangerous gases emissions from green
sands containing sea coal dusts, brown coal dusts, and not containing carbon addi-
tions are shown in Fig. 10.14.
In the cast iron foundry using green sands, nearly 90% of gases emission origi-
nates from mold pouring with liquid metal, from mold cooling, and from the opera-
tion of casting knocking out. The fraction of coal dusts in the greenhouse gases
emission in such foundry equals over 50%; especially it concerns CO2 emission.
The emission of the remaining greenhouse gases originates from the core thermal
decomposition, iron making, and other sources.
carbon Disulfide
Acetone
Heptane
Hexane
100% Causticized
Lignite
HAP and VOC Compounds
1,3-Butadiene 100% Seacoal
1,2,4-Trimethylbenzene No Carbonaceous
Additive
o-Xylene
m,p-Xylene
Ethyl Benzene
Toluene
Benzene
0 200 400 600 800 1000 1200

Concentration (micrograms/mˆ3)
Fig. 10.14 Comparison of green sands, with no carbon, with sea coal, and with lignite. (Reprinted
by permission from Ref. [3])
268 10 Green Sands
Table 10.5 Comparison of work rates before and after the replacement of part of the coal dust
mixture of graphite (savings of materials 14%, reduction of benzene emission >50%)
Consumption and Consumption and
Parameter properties before properties after
Normal bentonite addition 62 kg/t Fe 58.5 kg/t Fe
Sea coal addition 23 kg/t Fe 14.5 kg/t Fe
Low-emission bentonite (with small 85 kg/t Fe 73 kg/t Fe
amount of sea coal)
Bentonite content 10% 9.5%
Moisture 4.3% 4.1%
Compactability 28% 24%
Wet tensile strength 0.25 N/cm2 0.26 N/cm2
Compression strength 0.232 MPa 0.227 MPa
Therefore, efforts are undertaken to limit emissions of dangerous substances

from green sands. Three methods can be differentiated:
1. Reduction of emissions: applying alternative substances forming lustrous carbon
but of a smaller harmfulness than coal dusts, mainly due to a smaller emission of
BTEX and PAHs. Companies producing bentonite mixtures developed their own
compositions of these mixtures, where coal dust was partially substituted by
other additions of a smaller emission of dangerous substances (Table 10.5) [33,
34, 51, 52].
2. Adsorption of aromatic substances from molding sands and their decomposition.
Dangerous aromatic compounds are adsorbed by substances especially added to
molding sands. In such way emissions of these gases outside a mold are avoided;
however wastes with adsorbed dangerous substances of a significant concentra-
tion are left in a molding sand. Separating these wastes is quite costly.
3. The advanced oxidation process (AOP) is applied for the oxidation (removal) of
some low-molecular organic compounds. This process is generally defined as
the oxidation process occurring in a hydrous phase, containing formation of the
so-called free radicals, mainly hydroxylic *OH, causing transformations and/or
decompositions of determined contaminations. These radicals are characterized
by a fast and not selective oxidation of several organic compounds. Substances
applied in AOP can react and degrade some organic compounds present in a
molding sand. When, e.g., molecular ozone and hydrogen peroxide are used as
oxidizers, the radicals which are joining with such contaminations as benzene,
toluene, and phenol are formed. The AOP method allows for the decomposition
of toxic and difficult for biodegradation contaminations (via intermediate prod-
ucts, i.e., alcohols, aldehydes, carboxylic acids), to carbon dioxide and water.
Hydroxyl radicals can be formed:
• As a result of UV radiation of hydrogen peroxide (H2O2), according to reaction:
H 2 O2 + h½→ 2 * OH

• Under the ozone (O3) influence, according to reaction:
H 2 O2 + 2O3 → 2 * OH + 3O2
Hydroxyl radicals *OH react with organic compounds, e.g., by:

• Separation of hydrogen atom:
*OH + RH → R* + H 2 O
In such case alkyl radical (R*) is formed which, in the presence of oxygen dis-
solved in water, reacts with the oxygen molecule forming alkyl peroxide (RO2*)
radical:
R* + O2 → RO2 *
This radical undergoes decomposition, in result of which intermediate products

are formed. Further oxidations of intermediate products lead to the formation of
water and CO2.
In the case of methyl alcohol, this process is as follows [35, 53–57]:
O O
. . OH/O .
. . OH/O2 2 OH/O2
CH3OH + OH CH2OH H C H H C OH CO2 + H2O
Application of Additions Not Causing Emissions and Partially Substituting

Substances Forming Lustrous Carbon
These are the so-called low-emission technologies characterized by a lack or by a
very small emission of hydrocarbons [58]. The most advantageous is the substitu-
tion of substances forming lustrous carbon – used up to now – by inorganic carbon.
One of the more important coal dust substitutes is graphite, a natural carrier of
inorganic carbon (contains 70–95% of pure carbon). On account of difficulties with
the graphite dispersion in molding sands (graphite surface is hydrophobic and there-
fore difficult for wetting by water), it is necessary to develop the proper substance
dispersing graphite. In the presence of such a dispersing factor, graphite very uni-
formly covers surfaces of quartz grains (Fig. 10.15).
Graphite, in a similar fashion as coal dust, covers sand grains by a thin carbon
layer. Graphite, apart from preventing the liquid metal penetration deep into a mold,
is also acting as a lubricating compound and improves mechanical properties of a
mold. It is possible to achieve, in practice, reduction of BTEX emission from 50%
to 80%. Simultaneously other advantages occur: decrease of rejects amount,
decrease of wearing of additions containing carbon, and increase of efficiency
[56, 59–61].
Since green sands are mainly subjected only to rebounding, the return molding
sands from this technology are contributing to emissions of contaminations during
pouring, cooling, and casting knocking out. Additions of core sands should be mon-
270 10 Green Sands
Fig. 10.15 Effect of increasing lignite: sea coal ratio on (a) benzene emissions and (b) toluene
emissions. (Reprinted by permission from Ref. [3])
itored, e.g., by measurements of losses on ignition, since they are also causing the
emission increase. It is proved that the emission from cores with organic binders,
which are applied in green sands, sums up with the emission from green sands. In
the case of cores of sands with phenol – urethane resin the emission of HAPs from
the pyrolysis of core binders equals from 30% (for medium-core castings) to 70%
(for highly core castings) of the total HAPs emission from a mold [56]. American
Foundry Society (AFS) worked out the emission factors of hazardous air pollutants
(HAPs) for individual operations of the casting production, in dependence on the
kind of cores made of sands with organic binders [62]. Companies producing
foundry materials developed the so-called low-emission additives. Parameters of
especially prepared graphite with small amounts of coal dust are presented in
Table 10.5. Among others, 50% drop of the benzene emission is shown there.
Comparisons of these two technologies indicate not only advantages related to
the reduction of emitted gases but also to savings of materials.
When looking for substitutes of sea coal dusts, it should be remembered that
their main task is producing the oxidation atmosphere in the mold cavity followed
by the generation of lustrous carbon, which covers sand grains by a thin film. In
such way these grains are not wettable by liquid alloys, and occurrence of such
defects as buckles, rattails, etc. is limited. It is important to use additives which are
not generating emissions (or only minimal).
For many years of searching for the substitute of sea coal dusts, several sub-
stances, containing carbon and fulfilling the basic role, were tested. These were
anthracite, lignite, natural resins, synthetic resins, natural asphalt, coking coal dust,
graphite, and petroleum coke.
Presently, it seems that the best substitute is graphite in combination with an
adequate dispersing agent.
The S&B Industrial Minerals Company in cooperation with the University of
Technology in Freiberg, Jagiellonian University in Krakow, and AGH – University
of Science and Technology in Krakow developed the ENVIBOND technology, in
which the mixture containing bentonite, microcrystalline graphite, and zeolite was
applied. Due to that, the emission of VOC and BTEX was reduced to 50%. This
technology is already implemented in a few foundries in EU.
The results of investigations of gas emissivity from green sands containing vari-
ous lustrous carbon carriers (various grades of sea coal, brown coal, and resins)
and – for the comparison – the molding sand with ENVIBOND binder [34, 60] are
The measurement results of emission of substances from the PAH group emitted
from one of the tested molding sands under semi-technical conditions are presented
in Table 10.7.
The results of measuring emissions of substances from the BTEX group, which
were evolving from the mixture of sea coal dust with synthetic resin additions, in
dependence of the decomposition temperature are shown in Table 10.8. At a tem-
perature of 500 °C, the highest fraction in emitted BTEX gases had meta- and para-
xylene. Along with the increase of the decomposition temperature, the total
concentration of BTEX was increasing, mainly as the result of benzene and toluene
272 10 Green Sands
Table 10.6 Emission of gases from green sand with addition of different lustrous carbon formers
and content of BTEX
Volume of gases Emission of gases [mg/kg green sand]
(dm3/kg green
Sample sand) Benzene Toluene Ethylbenzene Xylene ∑BTEX
Green sand (1) 20.45 243.19 8.33 0.065 0.355 251.94 ± 25.19
Green sand (2) 19.12 386.73 9.76 0.13 1.20 397.81 ± 39.78
Green sand (3) 24.73 183.89 3.33 0.05 0.32 170.00 ± 17.00
Green sand (4) 22.19 392.65 16.44 0.06 0.50 386.90 ± 38.69
Green sand (5) 20.92 128.65 15.43 0.52 3.40 148.00 ± 14.80
(ENVIBOND
technology)
Table 10.7 Concentration of compounds from the PAH group in gases emitted from the green
sands and a substance forming lustrous carbon (semi-industrial tests)
μg/per kg molding μg/per kg molding
No Compound sands No Compound sands
1 Naphthalene 0.37 9 Benz(a)antracene <102.05
2 Acenaphthylene 4.48 10 Chrysene <26.6
3 Acenaphthene <0.19 11 Benzo(b)fluoranthene <21.16
4 Fluorene 20.72 12 Benzo(k)fluoranthene 19.83
5 Phenanthrene 585.33 13 Benzo(a)pyrene 7.53
6 Anthracene 605.52 14 Indeno(1,2,3-cd) 3.47
pyrene
7 Flouranten 632.84 15 Dibenzo(ah) <0.68
anthracene
8 Pyrene 428.72 16 Benzo(ghi)perylene <1.16
Total 2458.57 ± 490.35 μg/kg of green sand
Table 10.8 Concentrations of substances from the BTEX group in gases emitted during the
thermal decomposition of a mixture of sea coal dusts and synthetic resin, in dependence of the
temperature (decomposition in the air atmosphere) (Counted over for 1 g of sample)
Temperature (°C) mg/1 g sample
Compound 500 700 900 1100 1300
Benzene 0.4 5.0 30.8 39.0 6.70
Toluene 2.1 5.5 10.8 0.7 0.10
Ethylbenzene 1.4 2.6 1.2 1.6 0.7
o-xylene 0.0 0.8 5.9 0.4 0.2
m-, p- xylene 2.9 4.4 0.8 4.8 1.7
Total BTEX 6.8 18.3 49.5 46.5 9.4
concentrations increases. A sudden increase of the amount of emitted substances

occurred at the temperature range: 700–900 °C (benzene was the dominating com-
ponent). At the decomposition temperature of 1100 °C, nearly 90% of BTEX
substances constitutes benzene. At a temperature of 1300 °C, the emission of gases
is already small, but their main component is still benzene.
Leaching Into the Environment of Dangerous Substances from Spent Green
Sands
As the result of the liquid metal influence on green sands, containing additives gen-
erating lustrous carbon and cores of molding sands with organic binders, numerous
organic substances, which to a significant degree are getting out from the mold into
the atmosphere (during a mold pouring with liquid metal, mold cooling and casting
knocking out), are formed. However, certain amounts of them condense on sand
grain surfaces and remain in a molding sand in successive cycles, because the
rebounding process of green sands is not able to remove these molecules from the
grain surfaces. In successive cycles this molding sand is enriching in organic sub-
stances, which during mold pouring with liquid metal either undergo gassing or are
eluted, when spent sands are managed outside a foundry or stored on dumping
grounds. In both cases dangerous substances are entering into the environment.
Investigations carried out by S. Ji et al. [64] indicated very high contents of sub-
stances from the PAH group in spent green sands as compared with other molding
sands. Concentration of PAHs in spent green sands was from 9.36 mg/kg for steel
castings, 18.2 mg/kg for aluminum alloy castings, up to 28.7 mg/kg for cast iron
castings. The highest fraction in this group of substances had naphthalene, which in
every tested molding sands constituted app. 30%. Other organic substances identi-
fied in spent sands were hydrocarbons C14–C27, phenol, cyclic ketones, and fatty
acids. Their total concentration was equal to 98–120 mg/kg of sand.
Also metals were eluting from spent green sands; however their concentration in
a filtrate was quite small. The concentration of metals in filtrates from leaching of
spent green sands was in total (for 9 determined metals, As, Ba, Cd, Cr, Pb, Se, Ag,
Cu, Zn) for cast iron castings 0.920 mg/dm3, for steel castings 0.583 mg/dm3, and
0.950 mg/dm3 for sands originated from aluminum alloy castings. In this calculation
Cu is not taken into account, since this element is the alloying component.
Investigations performed with regard to the possibility of utilizing spent green
sands originated from producing castings of ferrous alloys in green sands and cores
with organic binders, in agriculture, or in terrain leveling indicated that concentra-
tions of such metals as Ba, Hg, Mn, Ni, and Pb can exceed allowable values for
drinking and underground waters [65].
On account of conditions which are in the green sand mold (sea coal dusts or
their substitute, cores with organic binders, oxygen and chloride ions – e.g., NaCl
present in coal dusts, high temperature) polychlorinated dibenzodioxines (PCDD)
or polychlorinated dibenzofuranes (PCDF) can be formed. These substances, which
are formed in combustion processes, are highly harmful. As the investigations of
R. Dungan [66, 67] indicated, these substances were identified in spent green sands,
however in amounts being near the minimal allowable values for the soil. Since
green sands as well as bentonite are of a natural origin, their source can constitute
the environment, or they can be of the anthropogenic origin.
274 10 Green Sands
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chemosphere.2009.01.080
Chapter 11
Other Molding and Core Sands
with Inorganic Binders
11.1 Geopolymer Binder
Binders based on mineral polymers called geopolymers are classified in the group
of inorganic binders for molding and core sands. Geopolymers belong to the alka-
line aluminosilicates group (they contain alkaline element sodium or potassium),
formed by long tetrahedral chains of SiO44− and AlO45−. These chains are connected
by common O2− ions into bi- or tridimensional lattice (Fig. 11.1). The negative
charge of fragments containing aluminum is equilibrated by metal cations. The geo-
polymers are not formed due to geological processes. Geopolymers are artificially
obtained, e.g., from fly ashes or slag. They are also called polysialate. These binders
undergo a gradual polymerization, since due to a hardener activity, the binder vis-
cosity increases and transformation into a solid substance – polymer of a high bind-
ing ability – occurs. The syneresis effect does not occur. The polymerization process
result is the inorganic solid polymer of a characteristic structure. The polymeriza-
tion proceeding of this binder is quite different than sodium silicate gelling process
in which the syneresis effect, i.e., liquid phase reducing from gel, occurs [1, 2].
Geopolymers demonstrate several advantageous features and therefore are find-
ing applications in many domains. Mineral polymers added to concretes cause sev-
eral times strength increase in relation to ordinary concretes, high fire resistance,
high resistance to the chemical compounds, and atmospheric factor influence. A
geopolymer binder is a clear, viscous liquid of a small polymerization degree and
amorphous structure [1, 2, 4, 5]. Due to the hardener influence, these binders
undergo a gradual polymerization, which causes a successive growth of viscosity of
a liquid and its transformation into a solid polymer of a high binding ability. This
binder is well water soluble. An application of various hardeners (most often it is a
mixture of organic esters) together with a temperature control allows to control the
polymerization process rate, and due to that, it is possible to control the molding
sand suitability time. The polymerization course of geopolymer binders is

278 11 Other Molding and Core Sands with Inorganic Binders
Fig. 11.1 Diagram of the

structure of geopolymer:
tetrahedrons SiO44− and
AlO45−. (Adapted from
Ref. [3])
c ompletely different than the gelling process of water glass [6, 7]. Water glass due
to the ester hardener actions forms – after the incubation time – practically in the
same time the elastic gel, in which the whole liquid phase is contained. Then the
syneresis effect occurs, i.e., the liquid phase educes from gel. Geopolymer binders
undergo gradual polymerization as the result of hardener actions (most often these
are liquids or CO2), which causes a successive increase of a viscosity of a liquid and
its transformation into a solid substance, i.e., inorganic polymer. Geopolymer bind-
ers in the system with a mineral matrix have a large cohesive strength, and their
destruction character is determined as adhesive, since a binder breaks away from the
matrix grain surface, while the structure of the binding bridge remains intact. Such
binding character facilitates the casting knocking out and spent sand reclamation [1,
4, 8, 9]. As the investigations of molding sands with geopolymer binders indicate,
they are characterized by a high strength, proper fluidity, and permeability [10]. In
addition, these sands are distinguished by good knocking out and reclaimability,
which constituted the main drawback of molding sands with water glass. In the case
of a molding sand prepared on fresh sands, the polymer binder addition equals
1.6–1.8%, and when a molding sand contains 75–100% of a reclaim, the binder
addition equals 1.8–2.0%. The mechanical reclamation can be applied for these
molding sands, and they do not require heating as molding sands with water glass.
A very important good point of geopolymer binders is their behavior at high tem-
peratures. In molding sands with water glass, the so-called first maximum of a
retained strength occurs at temperatures from 200 to 300 °C. Polymer binders do
not have, in this temperature range, any tensile strength increase. However, after
heating up to a temperature of 800 °C, the final strength of cores with geopolymer
binders equals 0.2 MPa; it means approximately five times less than of cores bound
by water glass only.
The GEOPOL® technology is currently used in the foundries for three basic pro-
duction technologies:
• Self-hardening molding mixtures for mold and core production
• Sand mixtures hardened by gaseous carbon dioxide for mold and core
production
• The hot-box technology with hot air hardening for cores
11.2 Water-Soluble Cores 279
Table 11.1 Volumes of gases and concentrations of substances from the BTEX group (mg/kg
molding sands)
Emission of substances from the BTEX group (mg/
kg molding sands)
Volumes of gases (dm3/kg molding sands) Benzene Toluene Ethylbenzene Xylenes
10.141 24.38 1.361 0.066 0.200
In this last technology, the hardening is caused by dehydration, so it means by a

physical process.
The GEOPOL® is odorless technology and generates no pollutants, so it has a
minimal negative impact on the environment [9].
Assessment of Harmfulness of Molding Sands with Geopolymer Binders
The measurement results of volumes of gases emitted at the mold pouring with
liquid cast iron of a temperature of 1350 °C, containing the core made of a molding
sand with geopolymer binder, are shown in Table 11.1. Volumes of gases and con-
centrations of substances from the BTEX group were measured [4, 11, 12]. The
maximum gaseous emission rate occurs in the first 50–80 seconds, from the start of
the mold pouring with liquid cast iron [12].
The emitted gases contained, in practice, only benzene from the BTEX group.
However, its concentration was approximately 20 times smaller than in the case of
some molding sands with bentonite and 10 times smaller than in the case of molding
sands with furan resins (Fig. 11.2) [9]. Therefore molding sands with geopolymer
binders should not be harmful for the environment and for employees. The presence
of the BTEX substances is a result of using a hardener containing organic sub-
stances. On the other hand, the GEOPOL® binder does not emit compounds from
the PAH group (Fig. 11.2) [9].
As it results from the performed investigations, the gas evolution rate from
molding sands depends on the binder kind and its content in the sand. Out of the
tested molding sands, the largest evolution rate characterizes molding sands with
resin-
based binders. Molding sands with inorganic binders (Rudal A and
GEOPOL@) indicate smaller evolution rate than sands with bentonite and
organic binders.
11.2 Water-Soluble Cores
Cores applied in a foundry practice are exposed in molds to significant thermal

and mechanical loads. Cores are subjected to an erosion caused by a high flowing
rate of liquid metal, undergo metal penetrations, and cause decreasing of a dimen-
sional accuracy of castings. Taking into account, as an example, the gravity die
casting and low-pressure and high-pressure castings, the pressure influencing the
cores gradually increases, and the cores must have higher and higher strength. When
Fig. 11.2 Results of pollutants (BTEX and PAHs) measurement during pouring, comparison of
organic and inorganic binder systems. (Reprinted by permission from Ref. [9])
traditional molding sand cores with organic binders – in amount of 1–3% – are used,
even 70% of all VOC emitting from foundry plants originates from cores.
An increase of the core strength causes a decrease of its compliance, which pro-
longs the time needed for its removal, and thus costs of the casting processing are
growing.
Numerous works aimed at minimizing negative features of cores with chemi-
cally bound binders led to the development of inorganic binders (sodium silicate
based) and salt cores (inorganic salts based) soluble in water.
Salt cores, on account of being soluble in water, are easily removable from
molds and indicate high compliance due to which they can take very complicated
shapes. Solubility of cores in water is especially important in the case of alumi-
num alloy castings, when too low temperature of liquid metal does not cause a
total burning of a core and additional operations are needed for its removal. Salt
cores have been known from the 1970s, but they were used only at multi-serial
production of aluminum alloy castings, e.g., cooling channels in valves of
engines cast gravitationally or under low pressure [13–15]. The production pro-
cess of salt cores and operations performed at high temperatures (pouring, cool-
ing, and solidification) do not emit VOC, which makes these cores
environment-friendly. These features of salt cores caused that they found wide
applications in automotive and aircraft industry, where castings of complicated
shapes were produced.
Water-soluble cores must fulfill the determined technological requirements in
order to achieve the optimal results [16]:
• Acceptable dimensional changes at their production, i.e., technological shrink-
age max. 2%.
• Dimensional accuracy should be ±0.2 mm.
• Adequate mechanical strength (bending strength minimum 3 MPa).
• Moisture resistance, both in vapor and liquid states.
• Not causing secondary defects in castings (reactions with metal, or surface
defects).
11.2 Water-Soluble Cores 281
Cores can be classified in dependence on:

• Production technology
• Chemical composition
Salt cores can be produced by various techniques, but the most often the described
below two technologies are applied:
(a) Sintering and pressing under a high pressure by using the recrystallization pro-
cess. When the core obtains the required strength as a result of joining wet salt
grains, it is followed by the recrystallization along grain boundaries. This
method of manufacturing cores has certain limitations concerning reproduction
of complicated internal spaces [17].
(b) Shooting into the core box the mixture with the proper inorganic binder and
hardening.
Another division of salt cores can be based on their composition, taking into
account mutual relations of water: water-soluble substance [13].
(a) Cores produced mainly of water-soluble substances, e.g., binary systems:
NaCl–Na2CO3; KCl–K2CO3; and KCl–NaCl, which strength is above 30 MPa
[18].
(b) Cores containing mainly water-soluble substances and some other materials
uniformly distributed in a water-soluble substance, e.g., mixture of melted
Na2CO3 and ceramic molecules of MgO [13].
(c) Cores produced mainly of fire-resisting materials, which form a binder with a
water-soluble material, e.g., zirconium sand and sintered powdered Al2O3, as
main components mixed with NaCl as a binder. Their strength was above
1.2 MPa [19].
Most often the mixture of Na2CO3, KCl (melting point 772 °C, boiling point
1407 °C), and NaCl (melting point 801 °C, boiling point 1465 °C) is applied. After
melting this mixture is used for making cores. Due to this, cores obtain the high
compression strength and dimensional stability, very much needed for producing
responsible castings. The drawback of such mixture constitutes its tendency for
forming shrinkage cavities, microporosities, and hot cracks. Hot cracks can occur in
salt cores when there is a volume change, e.g., during solidification. In addition,
cores are subjected to erosions caused by a high rate of mold filling with liquid
metal, by a metal penetration, and by worsening of dimensional accuracy when the
liquid metal temperature is approaching the salt melting temperature [20]. Therefore
special additions, of specific features and a determined granulation, are introduced
into the mixture of pure salts. These additions increase a thermal strength of a core
and decrease a possibility of surface defects on castings. Cores are often of compli-
cated shapes. In such cases the mixture of components is melted, and the obtained
homogenous liquid is injected into the metal mold under a high pressure. After
solidification a salt core is taken out from a mold. Such cores are applied in the die
and gravity castings.
On the other hand, for cores applied under high pressures, four-component
binary systems were developed [21]: NaCl–Na2CO3, KCl–K2CO3, KCl–NaCl, and
K2CO3–Na2CO3. Strength of cores made of a mixture NaCl–Na2CO3 was above

20 MPa at Na2CO3 content of app. 20–30% and 50–70%. The highest strength for
the system NaCl–Na2CO3, equaled 30 MPa, was obtained at 70% of Na2CO3 [18,
21]. As the research of Jiang, P. et al. [22] indicates, very good properties were
obtained for water-soluble cores composed of a mixture of MgSO4 (magnesium
sulfate) and Na2SO4 (sodium sulfate), hardened by microwave heating.
Two parameters decide on the salt core quality: the resistance to a moisture influ-
ence (service life) and a solubility. An addition of 3% of kaolin into potassium car-
bonate solution increases two times the tensile strength of cores and decreases the
moisture absorption rate by 14% [13]. These cores have a low emission of gases
(9.5 ml/g). The water-soluble core can greatly improve the production efficiency of
complex castings. This process has greater prospects in forming magnesium alloy
castings [20, 22].
Acknowledgments This chapter was done as part of the LIFE17 ENV/FI/173 Green Foundry
LIFE project (2018–2021).
References
Geopolymer Binder
1. Pezarski F, Izdebska-Szanda I, Smoluchowska E, Świder R, Pysz A (2011) Application of

molding sands with geopolymer binder in the manufacture of castings from aluminium alloys.
Trans Foundry Res Inst 2:23–34
2. Okoye FN (2017) Geopolymer binder: a veritable alternative to Portland cement. Mater Today
Proc 4(4):5599–5604
3. Davidovits J (2015) Geopolymer chemistry and application, 4th edn. Institut Géopolymère,
Saint-Quentin
4. Drożyński D, Bobrowski A, Holtzer M (2015) Influence of the reclaim addition on properties
of molding sands with the GEOPOL bonder. Arch Foundry Eng 15:138–142
5. Duxson P, Fernández-Jiménez A, Provis JL, Lukey GC, Palomo A, Van Deventer JSJ (2007)
Geopolymer technology: the current state of the art. J Mater Sci 42:2917–2933. https://doi.
org/10.1007/s10853-006-0637-z
6. Simonsen ME, Sønderby C, Søgaard EG (2009) Synthesis and characterization of silicate
polymers. J Sol-Gel Sci Technol 50:372–382. https://doi.org/10.1007/s10971-009-1907-4
7. Polzin H (2012) Anorganische Binder. Fachverlag Schiele & Schön GmbH, Berlin
8. Müller J, Stötzel R (2008) New innovative solutions for foundries by inorganic concepts. 68th
WFC–World Foundry Congress, Chennai, India, pp 133–136
9. Vykoukal M, Burian A, Přerovská M (2019) Geopol®. The innovated environment friendly
inorganic binder system. Arch Foundry Eng 19:109–119
10. Pezarski F, Smoluchowska E, Izdebska-Szanda I (2008) Application of geopolymer binder in
manufacturing of casting from ferrous alloys. Trans Foundry Res Inst 2:19–34
11. Holtzer M, Kumon S, Dańko R, Kmita A (2013) Elution of mixed molding sands with the
GEOPOL binder and core sands with the phenolic resin. Arch Foundry Eng 13:53–56
a new generation of core and molding sands. AKAPIT, Kraków. (in Polish)
References 283
Water-Soluble Cores
13. Zhang L, Zhang L, Li Y (2016) Effect of kaolin on tensile strength and humidity resistance of
a water-soluble potassium carbonate sand core. China Foundry 13:15–21
14. Czerwiński F, Mir M, Kasprzak W (2015) Application of cores and binders in metalscasting.
Int J Cast Metals Res 28:129–139
15. Beno J, Adamkova E, Miksovsky F, Jelinek P (2015) Development of composite salt cores for
foundry applications. Mater Technol 49:619–623
16. Tomek L, Lanik B, Sedlacek J, Vinter V (2012) Water soluble cores for aluminium investment
casting. Slevarenstvi 60:358–364
17. Stinii P, Schller G (2009) Leicht und rueckstandsaf Entkeruguss. Giesserei-Rundschau 6:4–8
18. Yaokawa J, Miura D, Anzai K, Yamada Y, Yoshii H (2007) Strength of salt core composed
of alkali carbonate and alkali chloride mixtures made by casting technique. Mater Trans
48:1034–1041
19. Jiang W, Dong J, Lou L, Liu M, Hu Z (2010) Preparation and properties of a novel water
soluble core material. Mater Sci Technol 26:270–275
20. Jelínek P, Mikšovský F, Beňo J, Adámková E (2013) Development of foundry cores based on
inorganic salts. Mater Technol 47:689–693
21. Yamada Y (2011) Method of manufacturing expendable salt core casting. Yamaha Patent US
2011/0062624 A1
22. Jiang P, Liu F, Fan Z, Jiang W, Liu X (2016) Performance of water-soluble composite sulfate
sand core for magnesium alloy castings. Arch Civ Mech Eng 16:494–502
Chapter 12
Protective Coatings for Mold and Core
Sands
When a mold is filled with molten metal, its surface is subjected to thermal,
mechanical, and physical–chemical influences. There is a possibility of reactions
between the metal oxidation products and mold materials, in the result of which
compounds of low melting temperatures are formed, e.g., silicates (when high-sil-
ica sand is a matrix), ferrous (the so-called fayalite Fe2SiO4), or manganese
(MnSiO3 or Mn2SiO4). This effect promotes a liquid metal penetration into inter-
granular spaces as well as capturing these products into casting surface layers,
which later require additional works at casting cleaning. In order to decrease this
effect and to avoid other defects (veins, burn-on, buckles), protective coatings are
applied on molds and cores [1].
The basic function of a coating constitutes providing the best casting surface and
minimal singe defects caused by the liquid metal penetration (by means of decreas-
ing capillary diameters in a mold and by changes of a liquid metal surface tension).
The application of fire-resisting coatings on cores is the basic condition of
obtaining the casting surface of a required quality. As far as the requirements of
customers are growing, the function of coatings becomes more and more impor-
tant [2].
The casting quality improvement, at applying fire-resisting coatings, is the
effect of:
• Decrease of capillary diameters in molding and core sands, thus preventing the
liquid metal penetration deep inside a mold
• Improvement of the resistance to erosion caused by a liquid metal stream
• Decrease of molding sand adhesion to the casting material
• Preventing formations of folds and cracks on surfaces of molds and cores
• Increase of a strength of surface layers of molds and cores
The properly selected fire-resisting coating provides the following benefits [3]:
• Reduces costs of casting cleaning, due to the improvement of a casting surface
quality

286 12 Protective Coatings for Mold and Core Sands
• Improves the casting knocking out

• Shortens the time of a casting mechanical treatment and decreases tool wearing
According to Campbell [3], coatings are not usually required in the case of cast-
ings of metals of lower melting temperatures, such as alloys of zinc and light metals
(based on Al and Mg). However they are widely used. Protective coatings applied
for molds and cores, apart from the listed above general features, can be character-
ized by specific properties in dependence on their destination and function. These
can be [4]:
• Passive coatings, which main aim is to provide a good casting surface.
• Strengthening coatings, which improve some properties of surface layers of
molds and cores, among others; they decrease a sand friability.
• Active coatings, which aim is the change of properties of the casting surface
layer (e.g., the coating containing CaO protects castings of spheroidal cast iron
against diffusion of sulfur from molding sand with furan resin hardened by sul-
fonic acids).
It is also possible that the given coating has simultaneously a dual function.
Coatings can be deposited in a solid form, as a paste or liquid.
Coatings deposited as dry substances are less often applied than wet deposited
coatings. Their main components are mica, white talc, and wheat flour. They are
blown on surfaces of cores or molds. On molds of molding sands with bentonite,
special coatings containing 80–90% of graphite (granularity below 75 μm) are
used [5].
Coatings deposited in a liquid form – two types, in dependence on a kind of
the applied molding sand and on the kind of alloy used for coatings, can be sin-
gled out. These are carbon-based coatings and coatings without a carbon. Carbon
coatings contain graphite, anthracite, and coke. Carbonless coatings can contain
mica, quartz flour (melting temperature 1734 °C), zirconium flour (melting tem-
perature 2727 °C), graphite, olivine (melting temperature app. 1800 °C) magne-
site, tale (melting temperature 1500 °C), and bentonite. Water or organic solvents
are used as carriers for wet deposited coatings. A liquid carrier constitutes
20–40% of a coating weight. When water is a carrier, the coating should be
dried, while when an organic solvent is used, it either evaporates or is burned.
However, during this operation VOCs are emitted. Isopropyl alcohol is most
often used as an organic solvent. This alcohol is fast drying and slowly burning
with small flames, which allows to avoid a local overheating of molding sands.
In addition, isopropyl alcohol is compatible with a majority of applied resins and
solvents [6].
According to the EU Directive [7], organic substances should be eliminated from
production processes, and due to that, foundry plants must apply water coatings
which, apart from advantages, have also several disadvantages.
The advantages of water coatings are:
• Higher safety in using, since they are incombustible.
• Environment-friendly because of a small VOC emission.
12 Protective Coatings for Mold and Core Sands 287
• Cheaper than alcohol coatings – cost reduction.

• In a majority of cases, a better surface of casting is obtained.
The disadvantages of water coatings are as follows [3]:
• More time and space is needed when they are applied (it is difficult to remove
water when core or mold is of a complex shape).
• The need of the special line for drying cores.
• Short lifespan of a coating, due to bacteria growing and unpleasant smell
occurrence.
• Decreasing of a tensile strength of molding sands with polyurethane resin no-
bake, cold-box, and water glass,
• Danger of damaging cores during storing and a possibility of water freezing.
• Since water coatings contain certain amounts of organic additions, their emission
can occur during casting knocking out.
• Water coatings can be dried in the air, in ovens, by means of microwaves or IR;
their drying time is longer than that of alcohol coatings.
Admittedly water coatings can be applied in a majority of molding sand tech-
nologies; however in certain cases, they cannot substitute alcohol coatings. Alcohol
coatings can be applied in the case of [5]:
• Large and complex cores or molds, due to difficulties in a warm air distribution
• Molding sands with water glass
• Casting of Mg alloys (water forms there Mg (OH)2)
• Producing castings of manganese steel at the MgO coating
Protective coatings for cores and molds consist of fire-resisting grain matrix,
binder, density stabilizer, and diluent. Sometimes special additions are also used.
Materials of a high melting temperature are applied as grain matrices, but they
should be also characterized by other features (Table 12.1). They should not react
with liquid metal, nor be wetted by liquid metal. They should not contain compo-
nents causing emission of gases, and they should have grains of the proper size
(50 μm and below) [3], shape, and distribution. A matrix coarseness decides on the
coating porosity; it means on the possibility of a liquid metal penetration deep into
a mold or core. Apart from pore sizes, the surface tension and metallostatic pressure
of liquid alloys influence this penetration. At cast iron castings, components con-
taining carbon, e.g., graphite, are added to matrices.
Coatings, especially water coatings, must contain stabilizing additives, which
allow maintaining binder components (of a various specific gravity) in a suspension
form and prevent a separation of components during their storage. Most often ben-
tonite, cellulose derivatives, and clays are used.
Important components of protective coatings are additives binding individual
components as well as assuring good connections of coatings with surfaces of molds
or cores. Quite often these are the same substances which are used for binding
molding sands (resins, colloidal silica, bentonite). In addition, these substances
should provide the proper mechanical strength and abrasion resistance of coatings.
Table 12.1 Properties of some materials applied as matrix of coatings for cores and molds
Chrome–
Parameter Chamotte Chromite Magnesite magnesite Quartz Corundum Talc
Refractoriness 1780 1850 1850 1850 1700 2000 1550
(°C) approx.
Thermal 0.0052 0.007 0.014 0.012
expansion
(×1000 mm/m)
Thermal 6–9.5 9–15 20–30 13–20
conductivity
(WK−1 m−1)
Density (kg/m3) 1800– 2600– 3900– 2580–
2150 2700 4100 2830
Wettability with No No No No wetting
molten metal wetting wetting wetting
The amount of binding additions should be optimal, because when it is too high,
especially when these are organic substances, it causes an excessive emission of
gases and a possibility of pilling and cracking of coatings after drying.
Often surface active substances, which by decreasing the interphase tension
facilitate the coating penetration to a proper depth (but simultaneously promote a
destruction of cores/molds), as well as bactericidal and antifoaming substances
are added to coatings [1, 7]. In order to improve the coating fire resistance, addi-
tions of substances of nanometer dimensions are used. In the case of aluminosili-
cate coatings, nanoparticles of boehmite (AlOOH), in amounts of 4–5%, are such
additives. This boehmite, at high temperatures, accelerates the process of forma-
tion of high-temperature phase of mullite – 3Al2O3·2SiO2 in the coating, during
the liquid metal reaction with a core/mold. After being heated to a temperature of
app. 285 °C, boehmite undergoes transformation forming nanomolecules: γ −
Al2O3 [8]:
2 ( γ − AlOOH ) → ( γ − Al 2 O3 ) + H 2 O at 285 °C

According to J. Campbell [3], the most advantageous is the situation; when there
is no necessity of using the protective coatings for molds and cores, it means when
the applied matrix of molding sands assures a good quality of a casting surface. He
mentions the following reasons of avoiding the protective coating application:
• Costs, especially when expensive materials are used as matrices, e.g.,
zirconium
• Difficulties in maintaining the required dimensional accuracy, since it is difficult
to measure the protective coating thickness
• Additional space needed for the stand of depositing protective coatings
• Costs of energy necessary for drying water coatings
• Time needed for drying decreases the production efficiency
Protective coatings applied on molds and cores contribute – to a significant

degree – to achieving good-quality castings; however they also constitute the
potential source of defects in production process, such as metal gassing, nonmetal-
lic inclusions, or buckles. Therefore, several investigations concerning modified
additions for molding sands, which would allow to avoid certain defects and simul-
taneously would substitute protective coatings, have been performed in recent
years. These additions mixed with a binder and sand provide a mixture, which
ensures the proper quality of casting surfaces, without applications of coatings.
The substitution of protective coatings by these additions contributes to production
costs decreasing.
Another important – possibly the most important – advantage constitutes the fact
that by avoiding the application of protective coatings, one or two technological
operations are eliminated (deposition of coatings, drying). This should contribute to
shortening the production time and thus to increase its efficiency. Abandoning of
alcohol coatings increases safety of works and protects the environment [9, 10].
Liquid Metal Penetration
Coatings have an essential function in preventing the liquid metal penetration into
molds or cores, which often leads to surface defects of castings [11].
There are four mechanisms of penetration:
• Mechanical penetration
• Chemical penetration
• Penetration in a vapor state
• Explosive penetration
Mechanical and chemical penetrations are responsible for 95% defects of cast-
ings. The metal penetration [11, 12] occurs when metals or metal oxides are filling
intergranular spaces not causing displacing of grains from the mold–metal bound-
ary. This effect depends mainly on the liquid metal temperature, interphase tension,
and metallostatic pressure. The metal penetration causes formation of bears of irreg-
ular shapes (being a molding sand and metal mixture) strongly adhering to a cast-
ing. Another characteristic defect constitutes veins – caused by a molding sand
expansion – which initiate the metal penetration.
Intergranular spaces can be treated as capillaries. When the capillary pressure is
lower than the metallostatic pressure, the mechanical penetration will occur. In the
case of cast iron, where there is a high content of C and Si, the surface iron will not
oxidize, and the mechanical penetration will not occur. Carbon will oxidize as the
first one forming CO, which is released from the phase boundary.
When the metallostatic pressure exceeds a certain limit value, molten metal
enters the molding sand structure, which results in worsening the surface quality.
Comparison of the surface quality of castings with the protective coatings and with-
out them at different metallostatic pressures is shown in Fig. 12.1 [13]. In this case,
the surface quality worsens when the metallostatic pressure exceeds 350–500 mm
of a metal column height (Fig. 12.1). It confirms the necessity of applying the pro-
tective coatings [13].
Fig. 12.1 Comparison of the surface quality of iron casting with and without protective coatings
at different metallostatic pressures ( “O”, samples without protective coating; “1,” samples with
commercial protective coating; “2” and “3” – samples with experimental protective coating).
(Reprinted from Ref. [13])
When the chemical reaction occurs between metal and matrix or between metal
and atmosphere at the mold–metal boundary, the chemical penetration takes place.
In the case of steel castings, most often fayalite Fe2SiO4 (melting temperature:
1200 °C) is formed on the casting surface. In the case of molding sands with ben-
tonite, with resins, and with water glass, after molds pouring with liquid metal, the
atmosphere at the mold–metal boundary should consist mainly of H2, CO2, and
CO. These gases can react with steel:
Fe + CO2 → FeO + CO
Fe + H 2 O → FeO + H 2
1
Fe + O2 → FeO
2
FeO oxide, which is strongly wetting silica (wetting angle equals 21°), is formed
in this reaction. Pure Fe is not wetting silica (wetting angle equals 154°). FeO can
react and dissolve high-silica sand, according to a reaction:
2 FeO + SiO2 → Fe 2 SiO 4
Thus, fayalite is a product of the chemical penetration. Other oxides, e.g., MnO,
which also react with silica forming silicates (ortho- or meta-) of a low melting
temperature, can be also formed.
Deposition of Protective Coatings
The thickness of the coating layer is very important. Too thick layer can be the rea-
son of the coating cracking. It is recommended that the thickness of the protective
coating layer should be equal from a few tenth of a millimeter to a few millimeters.
The protective coating thickness depends on the kind of a casting alloy and on the
thickness of casting walls. Liquid coatings can be deposited by immersing, painting
by means of a brush, by sprinkling, or by spraying.
Fire-Resistant Sol–Gel Coating
The novelty within the protective coatings range is the application of the sol–gel
process for their formation. This technique – in relation to protective coatings for
molds and cores – was developed in the Technical University of Denmark [14, 15].
The sol–gel method is based on a slow dehydration of the earlier prepared sol of
the given material hydroxide, which causes the sol changing into the gel. The reac-
tion of alcoholates hydrolysis is used in this method:

( RO )n Me + nH 2 O = nROH + Me ( OH )n
where M, metal atom of a valence n; R, alkyl group.
The reaction products are hydroxide and alcohol. A determined amount of acid
is added into the emitted hydroxide in order to transfer it into a colloidal solution
(sol). Then it is roasted at temperatures 427–827 °C, and as a result, powders (e.g.,

of oxides) are obtained. This stage decides on dimensions and shapes of grains and
on a powder ability for roasting.
The sol–gel method is a versatile technique being used for synthesis of oxide
materials both crystalline and amorphous glasses in a form of monoliths, powders,
fibers, and layers of various thicknesses. The sol–gel synthesis occurs in a liquid
environment at temperatures much lower than typical reactions in a solid state.
This method is often used to obtain glass coatings, including the so-called hybrid
coatings, i.e., organic–inorganic coatings of interesting optical features.
The sol–gel method has several advantages as compared with other methods of
producing coatings and films. For instance, when the process temperature is too low,
it is possible to change the sol composition in order to cause changes in the coating
microstructure.
Protective coatings applied for molds and cores contribute – to a significant
degree – to achieving good-quality castings; however they also constitute a potential
source of defects expected in a production process, such as metal gassing, nonme-
tallic inclusions, or buckles. Therefore, investigations concerning modified addi-
tions for molding sands, which would allow to avoid certain defects and
simultaneously would substitute protective coatings, are performed in recent years.
These additions mixed with a binder and sand provide a mixture, which ensures the
proper quality of casting surfaces, without applications of coatings. On account of
their origin, these additions can be divided into organic, inorganic, and hybrid. Each
of these additions has specific properties. Organic additions are used, e.g., to avoid
defects caused by sand expansion. Inorganic additions, e.g., iron oxides and ceramic
materials, are applied to avoid defects caused by emissions of gases. The newest
generation of additives, the so-called hybrid additions, combines the abovemen-
tioned properties and is especially efficient in preventing vein formations. This new-
est generation of hybrid additives can also substitute expensive specific sands [16].
Substitutions of protective coatings by these additives contribute to lowering the
production costs.
Another important – possibly the most important – advantage constitutes the fact
that by avoiding the application of protective coatings, one or two technological
operations are eliminated (deposition of coatings, drying). This should contribute to
shortening the production time and thus to increase its efficiency. Abandoning of
alcohol coatings for water-based protective coatings increases safety of works and
protects the environment [13–16].
References
1. Ramrattan SN, Joyc MK (2010) Effects of coating thickness on thermal distortion. AFS Trans
118:143–150
2. Nwaogu EC, Tiedje NS (2011) Foundry coating technology: a review. Mater Sci Appl
2:1143–1160
References 293
3. Campbell J (2011) Complete casting handbook, 1st edn. Elsevier, UK

4. Sobczak J (ed) (2013) Founder’s guide. Technical Association of Polish Foundrymen, Cracow.
(In Polish)
5. Pursall FW (1970) Coatings for molds and cores. Applied science in the casting of metals.
Pergamon Press, Oxford
6. Pirkle FL, Podmeyer DA (1998) Zircon: origin and uses, Transactions, vol 292. Society for
Mining, Metallurgy and Exploration, Englewood
8. Nikolaichik Y, Kukui D (2014) The use of nanomaterials for the synthesis of high- temperature
phase in refractory coatings. 71st World Foundry Congress, Bilbao, Spain
9. Stotzel R, Yilmaz I (2016) A new concept for the addition of molding and core sands for the
production of castings without defects and without the use of coatings. Polish Foundrymen’s
Association, pp 138–139. (in Polish)
10. Prat J, Stotzel R, Yilmaz I (2014) Additives to reduce veining and avoid refractory coatings.
71st World Foundry Congress, Bilbao, Spain
11. Stefanescu DM (2008) ASM handbook. Casting, 15, 9th edn. ASM International, Materials
Park
12. Stefanescu DM (2008) The effect of mold/metal interface phenomena on the surface quality of
castings. 10th Asian Foundry Congress, Nagoya, Japan
13. Kmita A, Zych J, Holtzer M, Mocek J, Piasny S (2016) Ecological water-based protective coat-
ings for moulds and cores of iron castings. Metalurgija 55:589–592
14. Nwaogu U, Poulsen T, Bischoff C, Tiedje NS (2010) Influence of new sol-gel refractory coat-
ing on the casting properties of cold box and furan core for grey cast iron. Proceedings of 69th
World Foundry Congress, Hangzhou, China, pp 0648–0653
15. Tan ALK, Soutar AM, Annergreen IF, Liu YN (2005) Multilayer sol-gel coatings for corrosion
protection of magnesium. Surf Coat Technol 198:478–482
16. Sander V, Yilmaz I (2017) That certain something in the casing process. New hybrid additive
for more effectiveness and efficiency in casting production. Foundry Trade J 191:230–231
Part IV
Special Technologies of Making
Molds and Cores
Chapter 13
Alternative Methods Using in Mold
and Core Technologies
13.1 Evaporative-Pattern Casting
Liquid metal is poured into a mold, in which there is a pattern made of a material
which under an influence of a temperature undergoes evaporation. The most often
such patterns are made of foamed polystyrene. Generated gaseous products are
removed via the refractory coating of the pattern and grain matrix of a mold. The
first patent concerning the casting production with the application of evaporative
patterns was submitted in 1956 by H.F. Shroyer. He patented the usage of these
patterns placed in a traditional green sand. In the year 1964, M.C. Flemings applied
the technique of foamed polystyrene patterns in a molding sand without a binder
(pure sand) [1]. Presently, two processes using evaporative patterns are applied [2].
These are:
• Lost foam process (LFP)
• Full-mold process (FMP)
The difference between these two processes is such that in the LFP process a
sand without additions of a binding material is used, while in the FMP process a
sand contains a binding material (this can be a bentonite).
Patterns applied in these technologies are expendable since they are destroyed
after the mold cavity is filled with molten metal. The process starts from designing
in the 3D-CAD system and then creating the complicated pattern, which is made of
expanded polystyrene (EPS)1 (Fig. 13.1) or sometimes of methyl polymethacrylate
1
Expanded polystyrene (EPS), i.e., foamed polystyrene, is obtained by foaming of polystyrene
granules. Polystyrene is a polymer obtained in the polymerization process of styrene, originated
from refining of crude oil or from catalytic dehydrogenation of ethylbenzene (Fig. 13.1).

298 13 Alternative Methods Using in Mold and Core Technologies
Fig. 13.1 Formation of CH CH2

polystyrene
H
polymerization
C C
H H
n
styrene polystyrene
Fig. 13.2 Formation of polymethyl methacrylate
(PMMA)2 (Fig. 13.2), on special injectors. The pattern can be made of one part or
can be glued from a few parts.
13.1.1 Materials for Evaporative-Pattern Casting
Polymers out of which patterns for this technology are made must be relatively easy
for forming and must have proper physical–mechanical properties, responsible for
the mechanical strength of a pattern. Another problem constitutes a fast decomposi-
tion of polymers during the casting production.
Patterns are made of expanding materials of a low density, such as:
• White, foamed polystyrene of a density from 16 to 20 g/dm3
• Blue, foamed polystyrene of a density from 18 to 22 g/dm3
• Foamed polymethacrylate (PMMA) of a density of 25 g/dm3
Individual pattern elements are cut out from these materials. They are later
notched and glued to achieve the final casting shape, taking into account a metal
shrinkage.
Some iron foundries cannot use expandable polystyrene because, during the
decomposition at 1500 °C, too much lustrous carbon is incorporated into the cast
2
Methyl methacrylate (MMA) is used for a production of methyl polymethacrylate (PMMA), one
of the widely applied plastics, the so-called organic glass, known as Plexiglas. It is also applied in
a production of emulsions for paints and lacquers, cosmetics, and acrylic resins (Fig. 13.2).
13.1 Evaporative-Pattern Casting 299
pattern. Copolymer beads of styrene/methyl methacrylate or styrene/methyl meth-

acrylate/alpha-methyl styrene are used in stated expandable polystyrene beads [3].
The most often, foamed polystyrene is used. This material has several advantageous
features such as fast and total thermal decomposition with emitting gaseous and
liquid products, small volumetric mass, low price, and high dimensional accuracy
of patterns. The composition and quantity of products formed during the pattern
thermal destruction is very important. Polystyrene must be subjected to special pro-
cessing in order to obtain the proper material for patterns [4, 5]. Low-impact poly-
styrene, which is brittle and of a low resistance to increased temperatures (app.
70 °C), is used for producing foamed polystyrene. An initial polystyrene consists of
92% of carbon and 8% of hydrogen and its density equals app. 565 kg/m3. Foamed
polystyrene of an apparent density of 15–20 kg/m3 is recommended for making pat-
terns for the full-mold method. Such polystyrene has the following properties:
Bending strength 0.30–0.35 MPa

Impact strength 0.01–0.022 J/m2
Thermal stability Up to 70–80 °C
Expanding temperature 180–250 °C
Combustion temperature App. 328 °C
Sulfur content ≤0.1%
The ready pattern contains app. 97.5% of the air and 2.5% of polystyrene.
Krauze et al. [6] investigated the thermal decomposition of polystyrene in depen-
dence on the temperature and the kind of the atmosphere (air and nitrogen), apply-
ing various heating rates of a sample. Examples of TGA and DTG curves, obtained
in the air (1) and in nitrogen (2) atmosphere, are shown in Fig. 13.3.
The heating rate as well as the kind of the atmosphere is influencing the thermal
destruction of polystyrene. The activation energy value, which for polystyrene
equals 230 kJ/mol, decides on the course of the thermal decomposition. This
substance undergoes the thermal decomposition starting at a temperature of

350 °C. In the oxidizing atmosphere the whole decomposition process (beginning,
maximal rate, end) occurs at a temperature by 20–40 °C lower than in the neutral
atmosphere. The tested sample in the nitrogen atmosphere underwent decomposi-
tion in app. 98%, while in the air atmosphere in app. 92% [7]. The mold pouring
temperature should be higher than the styrene destruction temperature; it means it
should be above 600–650 °C. During the mold pouring, more than 99% of a pattern
material is decomposing and gaseous and liquid products are evolving. A volume of
emitted gases depends on the evaporation temperature and increases with its
increase. A higher density of a pattern material generates higher amounts of decom-
position products. According to Sokołowski et al. [8]:
• 90–120 °C polystyrene softens
• 160–240 °C polystyrene fluidization, decreasing the initial volume
• 320–450 °C depolymerization
• 450 °C degradation of the polymer structure and the material destruction
1
100 Ta = 404 °C
Rate of mass loos, mg/min

Sample mass, % mas.
1 - air
–1
Tmax = 414 °C
50
–2
2 - nitrogen
–3
Tmax = 441 °C
1
2
0 –4
0 200 400 600 800
Temperature, °C
Fig. 13.3 TGA and DTG curves of polystyrene in 1, air and 2, nitrogen atmosphere. Ta, tempera-
ture of the polymer decomposition beginning and Tmax, maximum temperature on the DTA curve,
in which the polymer decomposition rate is the highest. An exothermic peak also appears at this
temperature. (Reprinted by permission from Ref. [6])
In order to identify the emitted substances, FTIR and GC/MS analyses were
applied [6]. The FTIR spectrum analysis indicates that mainly aromatic substances
are products of the polystyrene thermal decomposition. However, also peaks indi-
cating the presence of alkyl groups (CnH2n+1), alkanes (CnH2n+2), and alkenes (CnH2n)
are seen. The FTIR spectra of the thermal degradation products of polystyrene,
obtained in the air atmosphere at various temperatures, are shown in Fig. 13.4.
The thermal degradation of foamed polystyrene in the oxidizing and reducing
atmospheres was investigated. A detailed identification of formed substances was
performed by means of the gas chromatography (GC). The main substances were
styrene, styrene dimer, and styrene trimer. A significant fraction in the thermal
decomposition products had carbon dioxide, toluene, ethylbenzene,
α-methylstyrene, 1,3-diphenylpropane, 1,2-phenylethylene, 1,4-diphenyl-1,3-bu-
tadien, and 2-phenylnaphthalene. Differences in the composition of products were
dependent on the atmosphere. Differences in the composition of products were
dependent on the atmosphere [9, 10]. The scheme of the decomposition of polysty-
rene macromolecule is shown in Fig. 13.5.
Main decomposition products of the polystyrene molecule, i.e., styrene and eth-
ylbenzene, present in a liquid fraction are formed due to cracking of carbon–carbon
bonds. Significantly less derivatives containing three carbon atoms in a side chain,
and molecules containing one carbon atom in a side chain (toluene) are formed.
A complete pattern with gating and supplying systems is covered by protective
coat, the most often aqueous, and then dried before being placed in the mold. The
process of sand bonding should be selected in such a way as to avoid absorbing
moisture by the pattern before its pouring with molten metal.
13.1 Evaporative-Pattern Casting 301
50
2
1
Transmittance, %
40 1070,97
unsaturated aromatic 671,37
HC
-CH2 cyclic HC 730,07 Toluene
CO2 -CH3 Benzene
30 -OH
1729,33
C=C
-CH2 aromatic
-CH3
20
2123,03
2167,13
10
4 3 2360,32
4000 3000 2000 1500 1000 400

Wave number, cm–1
Fig. 13.4 FTIR spectra of volatile products of styrene thermal decomposition in the air atmo-
sphere (decomposition temperature: 1, 300 °C; 2, 400 °C; 3, 500 °C; 4, 600 °C). (Reprinted by
13.1.2 Coats for Evaporative Patterns
Ceramic protective coats (usually 200 μm thick) are used for foamed polystyrene
patterns. These coats are of a key importance in controlling the processes of filling
molds with liquid metal and forming defects in castings. It is mainly done by con-
trolling the process of removal the pattern degradation products from a mold [12–
14]. A permeability of protective coatings has a significant influence on the
obtained castings quality. At too small permeability, the pressure in the evapora-
tion zone increases, which – on the one hand – slows the decomposition of foamed
polystyrene, while – on the other hand – can lead to a casting gassing. At too high
permeability, the pressure of gases insufficiently supports the coating layer and
sand matrix deposited on a pattern, which means that a danger of forming defects
on the casting surface is growing [1]. It is recommended to use protective coatings
of a higher permeability in consideration of large volumes of gases formed during
the thermal decomposition of patterns during the mold pouring with liquid metal.
At that time also, liquid products, which can be wicking into pattern coatings, are
formed [15]. A permeability of protective coatings can be lowered when pores,
which are in the coating, will be filled with liquid products. It should be expected,
that thicker coatings will absorb liquid decomposition products and removing
them from gas louvers, especially in case of aluminum alloys, which have lower
melting temperature than cast iron [16]. The absorption of the thermal decomposi-
tion products of a pattern by liquid metal can cause casting defects such as folds,
porosities, and incomplete fillings (due to a premature solidification of a liquid
metal front) [17, 18].
As numerous investigations indicate, a higher permeability of protective coats
allows for a faster removal of decomposition products, which leads to a faster
CH3
CH CH2 CH CH2 CH CH2 CH toluene
n
benzene
CH CH2 CH3 CH3

CH2 CH3
C CH2 C CH2
styrene ethylbenzene
α-methylstyrene cumene
CH CH2 CH3
propylbenzene indane
Fig. 13.5 Main decomposition products of the polystyrene macro molecules. (Adapted from
Ref. [11])
filling the mold cavity by liquid metal [19]. When a permeability of coatings is
very low or a liquid metal temperature is very high, the mold filling process can
be controlled by a back pressure. That time, large amounts of gases and the air
will be building in into louvers between the metal front and a pattern. The mold
cavity filling process will be controlled by the rate with which the fire-resisting
coating will allow the air and gaseous decomposition products to reach a sand/
molding sand [19].
13.2 Lost Foam Process (LFP)
The lost foam process (developed and patented in the year 1958 by Shoyer) is simi-
lar to the investment casting process, but instead of a wax, the foamed polystyrene
is used for patterns (Fig. 13.6).
13.2 Lost Foam Process (LFP) 303
3 D.CAD product Splitting of design into Casting simulation Design of foam

design foam pattern sections moulding tools
Manufacture of Manufacture of foam Assembly of foam pattern Assembly of foam

moulding tools pattern sections sections into final pattern pattern into cluster
Ceramic coating Dry coated cluster Sand filling and compaction Pouring of
of cluster molten metal
Removal of castings Shotblasting Casting separation

from sand
Fig. 13.6 The lost foam process (LFP). (Reprinted by permission from Refs. [20, 21])
This polystyrene has a low boiling point, which facilitates the pattern removal
process, since the wax melting operation can be avoided. Usually a few patterns
made of the same material, in dependence of their dimensions, are clamped (glued)
to the vertical gating system, forming a bundle, called “tree.” Patterns in a form of
“tree” are immersed in the aqueous, fire-resistant coating, which constitutes a bar-
rier between liquid metal and a sand in the moment of pouring. After drying, this
“tree” is placed vertically in the molding box and sprinkled by a pure sand, without
a binder. A resin of a low viscosity can be added into a sand to prevent deformations,
which could occur during a vibratory compaction. This sand is compacted by means
of three-axial vibrations around the pattern. Due to that, it accurately penetrates the
pattern, reproducing precisely every detail, which makes cores and their instrumen-
tation unnecessary. During the mold pouring with molten metal the pattern material
decomposes and metal fills the free space. The formed liquid and gaseous products
are transported via the thin and porous fire-resisting coat, deposited on the pattern
(usually up to 1 mm thick), and penetrate into a sand.
Products of the pattern thermal degradation are absorbed by liquid metal dur-
ing a mold filling, which can lead to forming various defects in castings, such as
folds, porosities, surface dimples, and incomplete filling (caused by a premature
solidification of the liquid metal front) [5, 22, 23]. The used sand, mainly high-
silica, must be characterized by a good permeability, in order to assure the evacu-
ation of gases formed at a pyrolysis. Usually a sand of AFS 35–50 type is used. An
interruption of the filling process can cause the mold subsidence. Therefore the
automation of the pouring process is often applied. After cooling, the casting is
knocked out from a mold, which is easy since a molding sand was not bound by
any binder. Cast elements are characterized by a good dimensional accuracy. This
technology can be applied for a casting production of all alloys in a medium-lot
and large-lot production. This process is not hazardous for the environment in the
moment of forming, but causes emissions of gases as a result of the pattern ther-
mal destruction during pouring and during casting knocking out. The lost foam
process allows producing complicated elements, which often could not be made
by means of other methods. Due to this technology, it is possible to design very
complex shapes of castings, which significantly reduces processing and mini-
mizes operations of joining. At each production stage the appropriate control must
be maintained, to assure obtaining the ready products of the required quality [20,
24, 25]. Refractory coatings deposited on patterns are very important in reflecting
casting shapes, since they constitute the working surface of a mold. Thus, the
quality of surface casting depends mainly on the protective coating. Protective
coats based on magnesium and aluminum silicates and on zirconium are mainly
applied.
The lost foam process differs favorably from other casting technologies by the
fact that:
• Cores are not used, even at very complex castings, there is not a dividing line
• Dry sand without a binder is used
• There is no danger of shifting the mold walls
Owing to the facts above, this technology is less energy consuming and of a
smaller emission of gases and dusts. Amounts of wastes are significantly reduced
(after casting, knocking out the sand is nearly pure and can be reused several times),
castings of a high dimensional accuracy and very good surface quality are obtained,
cost of labor is lower and work conditions in the foundry are improved.
A drawback of foamed polystyrene patterns is their small resistance to defects
and deformations, which can occur already at not very high temperatures (70–80 °C),
as well as during forming. Therefore instead of polystyrene, the patterns are often
made of foamed methyl polymethacrylate, which at an increased temperature
decomposes – nearly only – into gaseous products. It means that lustrous carbon is
not evolving as it happens in case of polystyrene patterns. The formed gases easily
flow through the high-silica sand layer, but their certain amount is condensing on
cold grains and – to some degree – fulfills the role of a binding material. In succes-
sive cycles of utilizing high-silica sand, sand grains are covering themselves by a
tight layer of condensation products and therefore, after a few cycles, the matrix
must be rebounded. Another possible drawback of this technology constitutes not
properly selected protective coat for patterns, which can lead to a liquid metal pen-
etration and a danger of pinholes forming.
When polystyrene patterns are applied, contaminations of steel castings by
carbon are possible. This is an effect of a high-temperature influence on polysty-
rene patterns. At a temperature of 500 °C, foamed polystyrene decomposes into
monomers: C8H8. At a further increase of a temperature, these molecules are
13.3 Full-Mold Process (FMP) 305
decomposing into lighter hydrocarbons, such as C7H8, C6H6, C2H4, and C2H2.
These decomposition products of patterns constitute a source of carbon, which
diffuses into steel castings, causing an increase of carbon, especially in surface
layers of the pattern [26].
The interesting technology is the RepliCast process, which is a combination of
the full-mold technology with the investment casting method. A foamed polysty-
rene pattern is covered by a ceramic sand of a thickness of 2–8 mm (a little thinner
than in traditional ceramic molds) [1], prepared of ethyl silicate and fire-resisting
material. A mold is sintered at 1000 °C, and along with a mold hardening the pattern
is burned. After annealing, a mold is placed into a molding box and sprinkled with
high-silica sand compacted by vibrations. Sometimes a vacuum is earlier connected
to strengthen these mold elements via which liquid metal is flowing. By applying
neutral ceramic molds, the possibility of defects caused by hydrogen emission,
which can be a problem in case of producing castings of high-alloyed steels and
Ni-based alloys, is limited. Castings of a weigh from a few grams to 3.5 mg can be
produced by this method. The minimal wall thickness equals 2.5 mm. The lost foam
technology can be applied for producing castings of all alloys, starting from alumi-
num alloys, in a medium-lot and large-lot production.
13.3 Full-Mold Process (FMP)
The full-mold process is the process in which patterns of foamed polystyrene are
also applied. It combines the process of casting to sand molds and the lost foam
process. The pattern is sprinkled with sand with an addition of a binding material.
This technology can be applied in production of very large castings of cast iron, cast
steel, and non-ferrous metals. The wall thickness of a casting can be within the
range of 5–1000 mm. High-silica coarse sands, of a small contents of clay and of a
very high homogeneity factor, are used [2]. The castings can be of a weight up to
50 mg. However, in order to produce so large castings, it is necessary to use a binder
(e.g., furan resin), to obtain the necessary molding sand strength. This process is
applied in the production of medium and large castings, both in the piece production
and in small series production.
Patterns are made of expanding materials of a low density. The complete pattern
with gating and supplying systems is covered by a protective coating, the most often
aqueous, and then dried before being placed in a mold. The compact protective coat-
ing is formed on the pattern surface. Such sand binding process should be selected
which would allow avoiding moisture absorptions by the pattern, before its pouring
by liquid metal.
This process is very friendly for the environment at the formation stage; how-
ever, at pouring with liquid metal and castings, knocking out gases is generated.
These gases are the effect of evaporation of pattern materials and a binder destruc-
tion. A very important problem is the selection of a sand of a proper permeability,
which would allow vapors and gases to leave freely the mold cavity.
In a similar fashion, as in case of the technology using molding sands without a

binder, it is necessary – in this technology – to pour the mold without any interrup-
tions to prevent its collapsing. For each mold a separate pattern set – made of foamed
polystyrene – is needed, since it is destroyed in the mold pouring process. At
manufacturing of large castings using two or more ladles and more pouring simul-
taneously is recommended. The advantages of the full-mold process are as follows:
• High accuracy of reflections
• Possibility of producing geometrically complicated castings
• Using cores is not needed
• A few elements can be joined into one casting
• Possibility of a molding sand thermal reclamation
• Easiness of removing castings from a box
Influence on the Environment of the FMP
In case of applying molding sands without binders (LFP), amounts of solid wastes
as well as emissions are reduced to a minimum. These technologies allow producing
castings of thinner walls and smaller riser heads, with very low dimensional toler-
ance, due to which an amount of melted metal is proportionally smaller. Cleaning of
castings and their mechanical treatments are less labor-consuming. Patterns for this
technology are made of foamed polystyrene or methyl methacrylate, containing
small amounts of pentane. They are glued and covered by mineral protective coat-
ings. Since expanded polystyrene (EPS) and pentane are pure hydrocarbons, organic
carbon is a product of their pyrolysis. In order to minimize emissions of organic
compounds formed during the thermal destruction of EPS, reheating of exhaust
gases is applied. Admittedly, it was found that exhaust gases from the LFP technol-
ogy contain more BTEX and formaldehyde, but since their emission occurs only
during the mold pouring with liquid metal, these gases can be easily caught and
neutralized. An energy consumption in the LFP technology is much lower than in
traditional casting methods. It is mainly a result of smaller energy needed for finish-
ing castings, melting and preparing of molding sands. Also the core production for
traditional casting methods is more costly than foamed patterns production.
Data concerning emissions of organic compounds from the aluminum alloys
foundry applying the LFP technology of a yield of 1.5 ton/h and from the foundry
applying green sands of a yield of 1.2 ton/h and using 1.9 ton/h of cores from the
cold-box technology are shown in Table 13.1. The LFP foundry has a dust removal
station and gas reheating installation, while the foundry using green sands has the
system of fabric filters. The LFP foundry, which has more efficient installation
purifying exhaust gases, has a higher level of BTEX and formaldehyde emission but
significantly lower level of organic carbon.
13.4 Ceramic Shell
This technology is applied for making precise castings by the Shaw’s method and
cast investment method.
13.4 Ceramic Shell 307
Table 13.1 Emissions from Green

aluminum alloys foundry Compound LFP sand
using LFP technology and
Benzene 35.33 8.5
green sand (g/1 mg of liquid
aluminum alloy). (Adapted Toluene, xylenes, ethylbenzene, styrene 354.67 18.58
from Refs. [21, 27]) Unidentified organic compounds 96.67 655.0
Total organic carbon (TOC) 857.33 1283.33
PAHs 1.45 1.13
Formaldehyde 18.00 2.08
Phenol 18.00 69.83
These technologies are characterized by minimized emissions of dusts during

forming and finishing as compared to traditional methods. The VOC emission is
also eliminated, since neutral ceramic molds do not emit gases. In addition, amounts
of wastes are smaller; however, there is a problem with the utilization of knocked
out ceramic sand.
13.4.1 Shaw’s Method
Precise castings of a very good surface quality and high dimensional accuracy are
produced by the Shaw’s method. On account of high costs of foundry materials, this
method is applied for production of elements which, in case of using another tech-
nology, would require the time-consuming mechanical processing. It concerns espe-
cially products for the aviation and machine industry.
Traditional molding sand applied in this technology consists of a refractory
matrix and binder, which until recently was hydrolyzed ethyl silicate (presently
more and more often aqueous solutions of colloidal silica are used) and a hardener
(factor facilitating gelling) [28]. After mixing these components, a liquid molding
sand is obtained, which after being poured into a molding box – in 4–12 minutes –
undergoes solidification and obtains properties similar to the ones of rubber (high
plasticity and elasticity). Due to this, it is possible to remove the pattern without
damaging the mold cavity. In order to achieve a high-quality casting surface, the
proper selection of the matrix is important (grain composition, chemical composi-
tion, purity, thermal stability, thermal conductivity coefficient). To obtain a final
mold hardening, alcohol is burned out from it, which occurs simultaneously with
water evaporation and thanks to that the mold achieves the proper strength. The final
stage of the mold preparation is its annealing in a furnace. This process is performed
at a temperature of app. 1000 °C, since only at this temperature an increase of the
molding sand strength occurs. For economical reasons two-layer molds are often
used. In these molds patterns are covered only by 20–50 mm layer of a ceramic
sand, while the remaining part of the mold is filled, e.g., with molding sand with
water glass hardened by CO2. That time only ceramic sand is heated, while heating
of the whole mold is avoided. In effect, the network of microcracks is formed on the
mold, due to which the mold permeability improves and resistance to dilatation
changes increases.
Until recently, binders used in the Shaw’s technology were based on alcohol
solution of hydrolyzed ethyl silicate (tetraethyl orthosilicate CAS 78-10-4).
Tetraethyl orthosilicate is obtained on the industrial scale in reaction of ethyl
alcohol with silica tetrachloride (SiCl4) in the presence of a substance neutralizing
acid, formed in this reaction (Eq. 13.1):
4C2 H 5 OH + SiCl 4 → ( C2 H 5 O )4 Si + 4HCl (13.1)

Ethyl orthosilicate is ester of ethyl alcohol and silicic acid. This substance – in a
pure form – has no binding abilities, but easily hydrolysis in water. In the result of
ethyl orthosilicate hydrolysis silica is formed, insoluble in water, chemically neu-
tral, and resistant to high temperatures.
The hydrolysis process is performed in acidic environment (HCl, H2SO4). Since
ethyl orthosilicate is not soluble in water, the hydrolysis process must be carried out
in the presence of solvent, e.g., ethyl alcohol, acetone. The orthosilicate hydrolysis
can be presented by a reaction (Eq. 13.2):

( C2 H 5 O )4 Si + 4H 2 O → Si ( OH )4 + 4C2 H 5 OH (13.2)
The formed silicic acid in a colloidal form is then changing into gel, which is
having good binding abilities.
Binders based on hydrolyzed ethyl silicate (Fig. 13.7) indicate high stability of
technological parameters as well as assure fast drying of individual layers of the
ceramic mold. The produced molds are characterized by good strength properties,
good permeability of gases and easiness of casting knocking out.
Tetraethyl orthosilicate causes irritations of mucous membranes of eyes and
nose, in persons subjected professionally to its influence. On account of limitations
in applying organic substances, including ethyl alcohol, development of water
soluble binders became necessary. In case of ceramic sands technology, these are
binders based on colloidal silicate. This is a sol of silicic acid, i.e., suspension of
colloidal SiO2 molecules in water. Silica gel, obtained after water evaporation from
a sol, is a factor binding sand grains. Colloidal silica-based binders are character-
ized by a good wettability of wax patterns, long storage time, and – the most
important – they are environment-friendly. However, they require much longer
times for drying as compared to alcoholic binders. Colloidal silica is obtained from
Fig. 13.7 Structure of C2H3

ethyl silicate (ethylene
groups are bound with O
silicon atom by oxygen
bridges) C2H3 O Si O C2H3
C2H3
water sodium glass. As a result of hydrolysis and polycondensation reactions,

silica is obtained and alcohol and water are evolving [29].
Additions of organic polymers aimed at the strength improving of not dried
ceramic coating, at shortening of drying times of successive coatings as well as at
decreasing the gelated silica concentration, are introduced into binders based on
silica gel [30–32]. Very important is a proper selection of the matrix, warranting
achievements of the highest quality of the casting surface. The most often as a
matrix, mulite (3 Al2O3·2 SiO2) of an average grain size 0.06–0.08 mm is used.
Refractory materials can be based on: MgO, ZrO2, CaO·ZrO2, SiO2·ZrO2, and
MgO·Al2O3.
Castings made by the Shaw’s method are characterized by the following
properties:
• Very high dimensional accuracy
• Possibility of producing thin-walled castings (walls of a thickness of 1.3–3 mm
can be obtained from cast steels)
• Very good quality of casting surfaces
13.4.2 Investment Casting
The investment casting method is a technology of accurate casting, widely applied

for producing small (from a few grams to a few kilograms), complex, thin-walled
castings of a high dimensional accuracy and precise elements of a very smooth sur-
face. This method is especially useful when the used metallic materials are difficult
for machining or – in practice – not workable and create difficulties in plastic work-
ing [33]. This technology is known from a few thousand years. Previously it was
applied for producing figures of gods, ornaments, and jewelry. Natural beeswax was
used for patterns and clay for molds. Products of bronzes, copper, and gold were
manufactured. The earliest known text describing this technology (Schedula
Diversarum Artium) dated from 1100 AD was written by Theophilus Presbyter.
This technology in modern times was developed due to its application in making
teeth crowns (end of the nineteenth century).
Presently this method is used for producing castings for the aircraft, armaments,
machine, automotive, electronic, optical industries, and for the needs of medicine;
however, artistic castings are still manufactured [34]. Producing of ceramic molds
by means of the investment casting method is based on cyclic immersing of the wax
pattern in liquid ceramic sand, sprinkling it with ceramic course material and drying
the obtained layer until the needed thickness and mechanical strength of layered
casting mold is achieved. The final stage of the forming process is the wax pattern
removal by its melting, usually in an autoclave [35]. Successive phases of this pro-
cess are presented in Fig. 13.8 [36].
Ceramic molds should be characterized by the following properties:

• Low thermal expansion, in a temperature range of 600–1500 °C
• Proper refractoriness
• No reaction between pattern mixtures and metallic alloy
• Stability of properties, proper strength, and permeability
Making of a Wax Pattern
The process starts from making the wax pattern by pressing a liquid melted wax into
a matrix made of plastics, rubber, or gypsum. A pattern obtained in such way is a
precise copy of the casting, which is to be made. At making small castings, few wax
patterns are fastened to the gating system (also made of wax), forming the so-called
tree. Then the wax pattern is removed from a mold, its dimensions are checked, and
the pattern is cleaned. Patterns are cleaned by aqueous or organic solvents and cov-
ered by wetting agent facilitating wax adhesion to ceramic suspension. Patterns can
Wax injection Taking out

Model assembly
wax model
Coating of the model Plastering Finished mould Dewaxing

of the model
Finished casting
Baking of the mould Break-out

Pouring
Fig. 13.8 Scheme of the investment casting process. (Reprinted by permission from Refs. [20, 21])
be also made of plastics and low-melting alloys [37]. For precise castings, under
industrial conditions, synthetic waxes are used, and patterns are made in metallic
matrices. Presently, to improve wax properties the mixtures containing a few com-
ponents, such as natural ester waxes, natural and synthetic resins, natural waxes,
and hydrocarbon waxes, are used. Additions of small amounts of polymers, such as
polyethylene, ethylene, vinyl acetate, and ethyl cellulose, are usually improving
strength [38].
Pattern Covering by a Liquid Ceramic Sand and Building of a Ceramic Mold
Liquid ceramic sands contain a binding material and very fine powdered refractory
material, reduced to a slurry form, due to a continuous mixing. Colloidal silica,
hydrolyzed ethyl silica or hydrolyzed sodium silica can be a binding material. The
technology selection depends on the technological reasons. In case of using ethyl
silicate, the drying process is faster, which significantly shortens the whole process
time. However in this case, vapors of ethyl alcohol are emitted which worsens the
work comfort. At applying aqueous binders this emission is avoided [21]. The basic
flours applied for preparing ceramic slurry are malachite flour, quartz, zirconium,
magnesium flours, and aluminum silica. In case of casting highly reactive metals
(ferrous, copper, titanium alloys), graphite, zirconium dioxide (ZrO2), or yttrium
oxide (Y2O3) is applied [38–40]. Until recently, ethyl ester of orthosilica acid (called
hydrolyzed ethyl silica) or colloidal silica (sometimes water glass) was generally
applied as a binder of a ceramic slurry [1].
Presently the EU countries, due to regulations concerning the elimination or
reduction of emissions of all volatile compounds – also ammonia vapors – into the
atmosphere, are limiting to a minimum the ethyl silica application. Thus, currently,
e.g., “aqueous” silica inorganic binder is used. The process of making castings by
means of the investment casting method is schematically presented in Fig. 13.8.
Substances facilitating wax wetting, antifoam agents, as well as substances increas-
ing the coatings strength are added to a ceramic slurry to improve its properties.
Usually, a ceramic slurry contains 60–80% of bowdlerized fire-resisting material,
5–10% solid parts of a binder, and 15–30% of a liquid phase [41]. After immersing
a pattern in a slurry, a ceramic layer of a thickness of app. 0.5 mm remains on a pat-
tern. This layer is sprinkled by a stucco and then hardened (most often by drying).
The finest fire-resistant materials (of a diameter from 0.1 to 0.15 mm) are usually
used to form the layer directly adjacent to a pattern, while medium and coarse
grained materials (from 0.5 to 1.5 mm) are used for building next layers. Schematic
presentation of zones in a typical mold used in the investment casting technology is
shown in Fig. 13.8. Each coating is dried for 3–4 hours, in dependence of the humid-
ity of the surrounding atmosphere. In the same way, successive layers and sprinkled
materials are deposited. This deposition process is continued up to the moment of
obtaining a ceramic mold of a satisfactory strength. The coatings building process
contains one or two ground coats, four to five strengthening layers, and a tightening
layer [42]. Then the wax is removed from the dried mold. This process is carried out
in an autoclave, where wax is melted. Hot air, hot water, or electric dryers can be
also used. Then molds are annealed in electric or gas furnaces at temperatures:
850–1000 °C, where chemically bound water is removed and the left over material,
used for patterns, burned out [43–45]. In the same time, sintering of the ceramic
material occurs, providing the shell mold structure, strong enough to resist the liq-
uid metal pressure. The annealing process provides a shell with a permeability nec-
essary for removal of gases generated during its pouring with liquid metal. The
mold permeability decreases when its thickness increases [38]. Ready shells, before
pouring are heated to appropriate temperatures, in dependence of the casting alloy.
After pouring with liquid metal and then cooling, the shell is dismantled and indi-
vidual castings are cut out from the main gate.
The following metallic materials are applied in the investment casting:
• Aluminum, copper, and magnesium alloys
• Ferrous alloys
• Ni- or Co-based super alloys and alloys
• Titanium alloys
The investment casting method allows obtaining castings of a high dimensional
accuracy and of a very smooth surface. It allows to eliminate mechanical machin-
ing. Castings finishing is often reduced to surface grindings [46].
In recent years, several authors draw attention to a possibility of mutual interac-
tions of liquid metals with ceramic materials of shell molds, which unfavorably
influence the casting surface quality and prolong time of its finishing. Mahimkar C
et al. investigated effects on the boundary: ceramic material – low-carbon alloy
steel. As the products of these influences, substances of the type Al-Si-Mn-O and
Fe-Si-Mn-O occurred. The penetration depth of these compounds was dependent on
the composition of the layer directly adjacent to a pattern and on the coat porosity,
at a constant pouring temperature and casting shape. The coat containing zirconium
in the pattern boundary layer had the smallest amount of mutual interaction prod-
ucts and a small penetration depth [38]. This effect is especially strong in case of
making castings of titanium and its alloys, since they are highly chemically reactive
(possibility of reactions with hydrogen, oxygen, and oxides of Al, Si, and Ca). As a
result of the liquid alloy interaction with a ceramic mold, a diffusion of oxygen and
metal elements from a mold into a casting takes place, and the composition of tita-
nium oxide and intermetallic compounds, the so-called α-case zone, is formed. This
weakens some mechanical properties of a casting. The probability of these reactions
occurrence on the phase boundary: ceramic mold/liquid metal is very high and
depends on the kind of material used for the mold. For example, producing titanium
castings in ceramic molds containing Al2O3 + 50% Ti efficiently reduces the forma-
tion of the α-case zone [47, 48].
Increasing demands from the aircraft and automotive industries for precise
castings of light magnesium alloys caused, that more and more foundries were
undertaking production of such castings by means of the investment casting tech-
nology. The main problem in achieving high-quality castings of magnesium alloys
is related to a high tendency of this element to react with ceramic materials,
applied in this technology. In order to limit these interactions, the application of a
controlled atmosphere in the mold cavity, by its blowing through with protecting
gas (e.g., by a mixture: CO2 + SF6)3 before pouring with liquid metal is recom-
mended. An increase of the pouring metal temperature as well as the mold heating
temperature increases the intensity of the reaction: mold–metal. Admittedly, low-
ering of these temperatures suppresses – or even eliminates – reactions on the
mold–metal boundary, but this happens at the cost of the alloy fluidity worsening,
which – in turn – can cause other casting defects, such as an incomplete filling and
cold drop. The application of binders not containing silica as well as ceramic
materials of a high chemical stability is recommended, to limit mold–metal reac-
tions [38].
Melting of AZ91D alloy under vacuum conditions was successfully performed at
the production of thin-walled castings (wall thickness below 2 mm). This technique
application improves the liquid metal fluidity and gives very good final surface of
castings [49].The mineral called zircon (zirconium silicate ZrSiO4), characterized
by a high fire-resistance and thermal stability, often applied as a suspension compo-
nent as well as a coarse grained matrix, has also certain drawbacks. This is a side
product, generated in the process of obtaining titanium oxide (TiO2) from heavy
mineral sands. Due to that, it contains certain mineral contaminations such as rutile,
apatite, ilmenite, and even phosphates of rare-earth elements, which can be the rea-
son of casting defects and are decreasing the zirconium silicate heat resistance, even
at its very small content. That is why, it is not very suitable for a boundary layer. In
addition, waste sands can be radioactive, because this mineral often contains radio-
active isotopes of uranium and thorium. Radioactivity of wastes, apart from a health
danger, causes increased costs of their storing [50]. Another material applied for
matrices is modified melted aluminum oxide. From the mineralogical point of view,
it is α-Al2O3 (corundum). Its main advantage is a minimal amount of contamina-
tions and a possibility of producing grains of various sizes and shapes. It has excel-
lent thermal and chemical properties, which prevent a glassing effect and migration
of alloying elements into ceramic molds. In addition, its high resistance to deforma-
tions at high temperatures makes possible to produce castings of a very narrow
dimensional tolerance. The additional advantage of melted aluminum alloy is its
compatibility with Na-stabilized binders.
The hazardous substances emission in the investment casting technology can
occur in two operations: covering patterns by liquid ceramic sand and in wax
removals.
Wax melting in the autoclave does not have a significant influence on the air
quality, but when a ceramic mold is heated in an oven, e.g., to remove the leftover
wax, catching and leading outside the generated gases is necessary.
Burning occurs often with the air depletion and therefore carbon black molecules
are formed, which should be caught and after-burned. Ceramic filters are very suit-
able for this aim, since they can withstand high temperatures of exhaust gases, but
this very modern technology is not yet widespread.
3
However, SF6 is a strong greenhouse gas contributing the climate warming and therefore its appli-
cation is limited in several countries. Other protective gases for the melting magnesium alloys are
looked for, e.g., Freon. HFC-134a.
A certain problem for foundries constitutes spent ceramic sands, which are not
suitable for reclamation and difficult to utilize. Attempts of preliminary crushing of
such sand and then utilizing it as an addition to a matrix of molding sands with
chemically bound binders were undertaken [51, 52].
13.5 Vacuum Molding (V-Process)
The vacuum molding process (V-Process) was developed in Japan in the twentieth
century. In this process, the bonding material of a type of clay or binder was – in
practice – eliminated. The factor bonding matrix grains is the created negative
pressure, while a traditional bonding material occurs only in a residual form as a
plastic foil. The sand is kept in between two polyethylene foils, due to a negative
pressure. This process constitutes a very small hazard for the environment and can
be applied for castings of a majority of ferrous alloys and non-ferrous metals
alloys [34].
However, on account of its lower efficiency than processes based on organic
binders (resins type), the V-Process is suitable for producing small and medium
production series.
The example of producing the mold half is presented in Fig. 13.9 [21, 53].
It consists of the following phases [21]:
• Pattern is attached to the airtight chamber, connected with the vacuum pump. A
pattern is deaerated by openings of a small diameter, connected to a vacuum
chamber
• Thin layer of polyethylene vinyl acetate (PEVA) foil of a thickness from 0.076 to
0.200 mm is heated to a temperature of app. 85 °C
• This foil, which expands under a heat influence, is deposited on a pattern and
kept there due to the created vacuum
• A molding box, allowing the vacuum creation, is placed on a pattern and filled
with dry sand
• This sand is compacted by means of vibrations. After obtaining a smooth surface
the second layer of PEVA foil is deposited
• The air is sucked out from the molding box and at the same time the airtight
chamber is connected to a vacuum. This vacuum stiffens sand and the mold half
can be put away; the negative pressure is of the order: 200–400 mmHg (27–
53 kPa); the second half of the mold is made in the same way, and then both
halves are joined and assembled together with a vacuum still connected
After joining two halves, the ready mold can be poured with molten metal; both
halves remain connected to a vacuum, up to a moment when the casting is cold
enough to be knocked out. This knocking out is done by disconnecting a vacuum.
Sand is poured out through a grid and can be reclaimed after previous dedusting and
separating from not burned foil [54]. Castings produced by this technique are char-
acterized by a high dimensional accuracy, with a tolerance ±0.254 mm for the first
13.5 Vacuum Molding (V-Process) 315
Fig. 13.9 Stages of vacuum forming. (Reprinted by permission from Refs. [21, 53])
millimeter and ±0.050 mm for next ones. Castings of a wall thickness up to 2.3 mm
can be produced. The V-Process is characterized by the following advantages:
• Very good quality of casting surfaces
• Very good dimensional accuracy
• No defects caused by a moisture content and gases
• Costly binders are not used
• Molding sand has an excellent permeability
• There are no emissions of harmful substances, relieved at a binder
decomposition
• Excellent reproduction of details
• Wastes are not generated, because 99% of sand is again directed to the
circulation
• Castings are easily knocked out from molds
• Pattern is not much used since it does not have a direct contact with sand
• There are none non-metallic inclusions in castings (originated from sand),

• Small operational costs,
• Small amounts of rejects,
• Possibility of utilizing for a majority of ferrous alloys and non-ferrous metals
alloys.
A certain drawback constitutes the fact that this technology requires special pat-
tern sets.
The V-Process is environment-friendly, it applies clean, dry sands, without bind-
ers, and the obtained castings are characterized by a high dimensional accuracy.
Used sand (after being knocked out from a mold) requires only cooling and trans-
porting from the shake out grid to a forming place, eventually dedusting and sieving
to separate metallic elements.
13.6 Frozen Mold
The process of making castings in frozen molds, called sometimes the frozen pro-
cess was developed in Great Britain by F. Hoult in seventies of the last century [55]
and simultaneously by V.M. Gruzman in the Soviet Union [56] and in Japan [57].
Varieties of this technology, developed in Poland, are called IGLOFORM. However,
this new technology did not find a wide practical application in times of its develop-
ment, due to a high price of liquid nitrogen, which was used as the basic cool-
ing agent.
In their simplest form, these molding sands contain only sand and water (in
proper amounts). This mixture is frozen and ice bridges in between sand grains act
as binders. There are a few varieties of this process, in which additions of clay or
bentonite and sometimes organic substances are introduced [57, 58].
This process has several good points as compared with other technologies of
molds and core production. The most important advantage of frozen molding sands
is a significant reduction of the environment pollution. Such effects as noises, vibra-
tions, and dusts emissions do not occur in practice during the casting knocking out,
since the mold – after being poured with liquid metal – is self-destroyed. As far as
the molding sand does not contain organic compounds, neither unpleasant odors nor
harmful substances evolve from the mold. In addition, this sand after being knocked
out can be directly turned back to the circulation (after supplementing water
amounts), which contributes to a significant reduction of wastes. Another good
point of frozen sands is the fact that such mold accelerates the casting solidification
process and due to that the casting achieves a finer structure [59, 60].
The improvement of the liquid metal fluidity is explained in the paper above.
Frozen sands generate more water vapors than green sands. This vapor locates itself
between liquid metal and a mold surface in a form of a thin film, causing a decrease
of the heat-exchange coefficient between sand and metal. To this effect, a drop of a
liquid metal temperature – immediately after pouring – is damped, and fluidity can
13.6 Frozen Mold 317
grow. Contrary, after the casting solidification, the cooling rate in frozen molds
increases (in relation to other technologies) since there is a higher temperature dif-
ference, which favors the structure refinement. Castings of Cu, Al, and iron alloys
can be made in frozen molds. Such two-component molding sand (sand + water)
has, however, some drawbacks:
• Very low strength in a wet state (before freezing), which makes the formation
process difficult
• Large energy consumption by freezing to the determined temperature.
The minimal strength in a wet state of two-component mixture makes impossi-
ble – in practice – to remove the pattern instrumentation before freezing. Therefore
another version of this process was developed, where additionally 2–5% of clay or
bentonite was introduced into the molding sand. Such mixture had already a suffi-
cient strength allowing to dismantle the mold. Such, preliminarily hardened mold,
is introduced into a chamber where it is subjected to the cooling agent influence, the
most often nitrogen. The schematic presentation of frozen molds process is in
Fig. 13.10.
Main technological properties (strength, permeability) of two-component frozen
molding sands depend, to a significant degree, on the freezing temperature and
water content. A strength of this mixture significantly increases as water addition
increases (optimal 5–7%) and as a temperature decreases (but only to app.
233–223 K). On the other hand, a permeability of frozen sands decreases as a water
addition increases.
The newest technique concerning frozen molding sand utilizes the cold air
pressed into the mold using liquid nitrogen. The frozen mold temperature equals
from −20 to −30 °C (Fig. 13.10). Molding sands produced by this method obtain
compressive strength of 5 MPa, at the composition: sand and 5% of water.
Sometimes, for the strength improvement of the frozen mold surface, especially
after its defrosting, instead of water a solution of colloidal silica is added (contain-
ing 30% of silica nanomolecules) [61]. A molding sand with addition of colloidal
silica has certain positive properties, among others, after defrosting it still has a
Fig. 13.10 Schematic illustration of the differential pressure mold freezing method. (Reprinted by
certain strength which is not falling drastically during recycling [60]. The devel-
oped, modern version of frozen molding sands indicates several advantages, which
can contribute to an easier utilization of this method in the industry. These are:
• Significant reduction of wastes, since the whole knocked out molding sand can
be reused
• Easy casting knocking out from a mold
• Fluidity improvements of casting alloys
• Refinement of casting microstructures
• Possibility of producing cores, even of very complex shapes, since they can be
easily removed from the casting
When a molding sand consists of sand and water only, then after knocking out,
the whole molding sand can be directed to recycling, after supplementing water,
without the need of additional treatments. An application of a finer sand matrix
improves the casting surface quality but decreases the molding sand permeability,
which can prolong the mold freezing time. An application of high-silica sands of a
higher content of clay and dusts fractions is advantageous. An increase of strength
is obtained at a sufficient permeability [1]. The frozen molding sand technique can
be used for producing molds as well as cores, which can be used in molds made of
different molding sands. These cores are easily removed from castings after their
knocking out, since they are completely disintegrated. The surface quality and
dimensional accuracy of castings produced in frozen molds are slightly better than
at the application of classic green sands [1].
13.7 Rapid Prototyping Technology
It seems that the method of producing castings in expendable sand molds, especially
in case of large and very large series production, in not to be substituted. However,
in case of small- and medium-lots, at a limited time when a fast designing and pro-
ducing of the prototype is needed, computer techniques are finding their applica-
tion. One of such techniques, accelerating production, is Rapid Prototyping (RP)
[62, 63].
Rapid Prototyping are techniques of a fast automatic production of machine ele-
ments and other objects by means of devices controlled by a computer, on the bases
of the previously prepared solid pattern, with disregarding traditional technologies
(mechanical, casting, decrement, and electro-erosion).
The notion “Rapid Prototyping” contains all technical and organizational opera-
tions, starting from the formulation of the product concept up to its production. The
base of the whole process is the digital 3D model made in the CAD environment.
On its base the real object is formed, due to utilizing the ability of joining various
materials such as plastics, paper, ceramics, metals, or composites.
RP is the additive method, which means that it is based on a gradual placement,
layer after layer, determined elements of three-dimensional space, on the bases of
13.7 Rapid Prototyping Technology 319
previously prepared 3D patterns. This technology allows for the accelerated passage
from the concept of the product to the ready casting. RP methods are intended not
only for making prototypes of certain elements but also for creating tools – rapid
tooling (RT) – and for creating ready products, rapid manufacturing (RM). RP can
be introduced at an arbitrary stage of the production process, i.e., at developing the
concept of the pattern, geometrical and functional, prototypes, as well as of techni-
cal or sale prototypes.
RP methods are very efficient in small series and in piece production. Due to
them, it is possible to shorten significantly the development cycle of the product, as
well as to decrease expenditures for its working out and implementing. The factor
decisive for the growing interest of these methods is the possibility of manufactur-
ing elements without producing special instrumentation, e.g., molds.
The full automation of the production process is essential. It is based only on the
computer 3D integration with the CAD system. Thanks to that, it is possible to
eliminate majority of problems related to traditional manufacturing processes, such
as, e.g., necessity of determining the geometry of semifinished products or planning
the technological process. RP provides a significant decrease of costs and time in
phases of the product development as well as in manufacturing ready products in the
piece and small-lot production [64].
All currently available technologies allow to make the prototype of a part on the
bases of three-dimensional drawing. They are also applied for a direct sintering of
molding sands in mold and core production. This technology is based on building
an object according to a drawing of the pattern, by joining its parts or layers of such
raw materials as polymer resin, wax, paper, or ceramic powder. Spatial printing
(3D) means forming a physical object on the bases of the CAD file only [62].
The RP technology makes possible a pattern production in a very short time,
which provides wide possibilities of this technology application. In contrast to dec-
rement methods used by machine tools, the RP method is additive, which means
that it is based on gradual placements of successive layers of a material by gluing,
sintering, or hardening by other substances or by laser [65].
The three-dimensional printing – 3DP – belongs to the group of RP technologies.
3D printing has the potential to supplement or partially replace the casting method.
Today, some castings can be directly printed by metal powders, for example, tita-
nium alloys, nickel alloys and steel parts. Meanwhile, 3D printing has found an
unique position in other casting aspects as well as in printing the wax pattern,
ceramic shell, sand core, sand mold, etc. [64, 66].
Three-dimensional printing of sand molds and cores is changing the casting pro-
duction way.
The Rapid Prototyping technology 3DP is realized in four steps:
1. Formation of the three-dimensional pattern by the CAD techniques
2. Forming of INTERFACE between 3D – CAD system and the Rapid Prototyping
system, e.g., the CAD data can be transformed into the STL format (Standard
Transformation Format)
3. Cutting of the STL file into thin lateral layers
4. Building of the RP pattern:

(a) Binder and sand are dosed on the printer with a micrometric accuracy and
bound layer after layer.
(b) The solution from the printer activates a binder which is bonding individual
molecules, the process is not finished until a mold or core is made.
(c) The manufactured mold or core is subjected to drying (sintering) in the fur-
nace for a couple of hours, and then they are ready to be poured.
The 3D sand mold printing process works similarly to traditional inkjet printing.
Drop of binder (phenol or furan) are spread on a fine layer of acid mixed sand and
then the polymerization takes place to bond the sand particles. The binder is only
spread in the required location and the bonding reaction take place. The platform
move downward by the set distance and the recoater spread another sand layer. The
process repeats until all the 2D slices of the 3D design are printed.
Introduction of 3D printing into sand mold production has many advantages:
• There is no need of making prototyped molds or costly operations by CNC
devices.
• After the designing phase, a visually ready core or mold can be made at once.
• Constructional-visual errors can be verified.
• Ready mold/core is characterized by a good knocking out ability and high dimen-
sional accuracy.
Three-dimensional printing of cores and molds has come of age [63]. One of the
reasons is generating, by the traditional technology of producing castings, signifi-
cant emissions of CO2, which is related to high costs. In the 3DP process, the reduc-
tion of CO2 emission equals at least 30–40%. The advantage of the 3DP process is
also a result of savings metal and chemical substances applied for manufacturing
molds and cores. The 3D printed investment-casting pattern can be produced in a
foundry at a cost of under 10% of the traditional production cost [67].
The introduction of 3D printing into the production of molds and sand cores
provides several advantages, such as saving of materials and raw materials, reduc-
tion of energy consumption, and reduction of CO2 emission. This method is espe-
cially suitable in castings of very complex shapes produced in small and medium
series. The molds and cores produced by SLS and 3DP methods have been success-
fully used to produce complicated castings such as cast iron and aluminum cylinder
blocks, cylinder heads, gear boxes, etc. [68–70]. Since costs of the production per-
formed by means of the 3DP technology are significantly dependent on prices of the
applied materials, intensive research considering this problem, with taking into
account the influence on the environment and on work conditions, is carried out [62].
Rapid prototyping techniques due to the material used can be divided into the
methods using [70]:
• Liquid material
• Solid material
• Powders
13.8 Natural Polymer-Based Composite Binders 321
13.8 Natural Polymer-Based Composite Binders
13.8.1 α-Starch-Based Binders
A binder consisting of not modified starch does not warrant that a molding sand will
have proper strength properties. However, with various additions, starch can be the
main binder component.
Cores of molding sands with bentonite modified by potato starch were success-
fully applied for making steel castings, iron castings, and aluminum alloys
castings.
The new binder containing α-starch (2.5–4.0%), kaolin (3.0%), sodium meta-
silicate (0.55%), dextrin (0.35%), and sodium phosphate (NaH2PO4 2H2O) (0.04%)
was developed [71, 72]. A molding sand hardening occurs as a result of a water
evaporation while a mold is heated for 1 hour at 160–200 °C. At the fraction of
2.5% of α-starch a molding sand was achieving a tensile strength of 1.4 MPa. As
the tests indicated, cores bound by this binder can substitute cores bound by
furan resin.
Admittedly at high temperatures, starch is decomposing, but other binder com-
ponents such as sodium silicate and sodium phosphate react with kaolin, forming
heterogeneous lattice Al-O-Si, containing the heat-resistant phase: AlPO4. Cores
bound by this binder were resistant to a temperature up to 1360 °C [72]. This
molding sand has a good resistant to moisture content nearly the same as a mold-
ing sand with furan resin, after a longer time and at a relatively high moisture
content. In addition, this molding sand is cheap, not much harmful for the environ-
ment, has a high strength in the dried state and can be recovering its resistance to
moisture content. Such high resistance to moisture content of this binder results
from its special heterogenic structure and bonds formed between a binder and
silica by coupled valence electrons [73, 74]. The molding sand with such mixed
binder has better properties than the one in which only α-starch is applied as
a binder.
High-temperature strain-stress curves of cores bound by starch, after heating to a
temperature of 1000 °C, are shown in Fig. 13.11. It seems that when strength at a
room temperature is satisfying, the content of starch should be decreased to improve
properties of cores at high temperatures.
A thermal degradation process of starch starts at a temperature of app. 280–300 °C
with a formation of ether bonds and releasing water molecules. This process is
accompanied by emissions of water vapor, CO2, CO, and aliphatic hydrocarbons,
e.g., CH4 (methane). Above 500 °C, at a limited oxygen access, the carbonization
process occurs as well as the intensity of aromatic compounds formation grows.
Starch heating at temperatures above 600 °C creates conditions for forming amor-
phous carbon [76–78].
Fig. 13.11 High-temperature stress-strain curves of cores manufactured with binder containing
α-starch. (Reprinted by permission from Ref. [75])
13.8.2 Collagen-Based Composite Binders
The example of this technology binders can be developed in early 1990s, hybrid
binder containing alkali silicate and hydrolyzed collagen [79–81]. Collagen is a
component of majority of tissues and organs of animals, among others: bones, car-
tilages, skin, and tendons. At a room temperature, it is characterized by a high ten-
sile strength, comparable with steel. However, at a high temperature its strength is
not sufficient to withstand metallostatic pressure and therefore it cannot be applied
as self-contained binder. But when alkali silicate (of sodium, potassium, or lithium)
is mixed with hydrated collagen, a strong bond, of advantageous physical and
mechanical properties is obtained (Fig. 13.12). This new hybrid organic/inorganic
binder has, at a room temperature, a higher tensile strength and higher resistance to
the liquid cast iron penetration than conventional binders based on phenol-urethane
resin or modified sodium silica.
The first step in the collagen preparation – as a binder component – is its penetra-
tion in water, which occurs at a temperature of app. 65 °C. Near this temperature a
gel starts forming. This gel is mixed with warm sand and alkali silicate, and the
obtained core sand is blown into the core box, heated to 130–180 °C. After a water
evaporation from gel the collagen structure becomes stronger (hydrogen bonds are
joining with polypeptide chains) and the core achieves the proper strength [80, 82].
This binder is characterized by a significantly smaller VOC emission than numerous
commercial organic binders. Its thermal decomposition occurs at a relatively narrow
temperature range of 250–500 °C. Within this range the molding sand losses
approximately 65% of its initial weight. Emissions of CO and CO2 occur at tem-
peratures above 600 °C, while hydrocarbons are mainly emitted within the range
13.8 Natural Polymer-Based Composite Binders 323
Fig. 13.12 Hot distortion test for cores manufactured with several types of binders. (Reprinted by
Table 13.2 Composition of Content (mas.%)

the sand mold in which furan Component Molding sand I Molding sand II
resin is substituted by PLA or
PCL Silica sand 100 100
Furan resin – 0.935–1.045
Activator – 0.55
PLA/PCL 1–4 0.055–0.165
Solvent CH2Cl2/acetone
300–600 °C, when the thermal destruction is the most intensive [83]. Emissions
from cores with collagen-based binders constituted app. 7–11% of VOC, hydrocar-
bons, and HAP emissions from cores with phenol-urethane resin (Table 13.2). At
the pyrolysis temperature of 929 °C this collagen binder was releasing 50–60% less
VOC as C6–C16 and 75–80% less HAP than phenol-urethane binder.
In order to obtain as good as possible properties of water glass, sodium poly-
phosphate was introduced apart from collagen. Cores hardened by the warm-box
technique had the following properties: tensile strength of 1.37 MPa, compression
strength of 2.16 MPa. Automotive castings of aluminum alloys produced by this
technology indicated that cores made fully of molding sand with warm-box hard-
ened binders can substitute cores with organic binders manufactured by the cold-
box method (applied up to the present). The developed composition was sodium
silicate 4–7%, collagen 1–2%, sodium polyphosphate 0.415–0.7%. The cores of
such composition were obtaining the best mechanical properties and could with-
stand temperatures of up to 159 °C. The produced steel castings had very good sur-
faces [75, 80, 84, 85]. When alkali silicates are mixed with hydrated collagen, the
bond, resistant to premature temperature influence and to decomposition, is

obtained. This new binder has at a room temperature a higher tensile strength and a
higher resistance to the liquid cast iron penetration than the conventional phenol-
urethane binder.
13.8.3 Binder Based on Polysaccharide
The cores produced as shell cores or by the cold-box technology, in case of alumi-
num alloys castings, are often creating problems at their knocking out, on account
of unsatisfactory overheating and destruction degree. Studies concerning the appli-
cation of polysaccharides as binders for such cores are carried out for a couple of
years [86, 87]. The new core binder based on polysaccharides named LYTE CORE
was developed in Japan. High-silica sand with a binder addition is intensively mixed
in a mixer to form air bubbles in a molding sand. Due to that, a suspension of a good
fluidity, which can fill even a very complex core box, is obtained. This suspension
is introduced under a pressure into a core box heated to the needed temperature.
Then moisture is vaporized and a molding sand is dried and hardened. Empty cores,
which are easily knocked out from castings of aluminum alloys, e.g., by vibrations,
are produced by this method. Knocked out molding sand, after removal of binder
leftovers and dust fractions, is returned to the circulation. Cores obtain a bending
strength of above 4 MPa (at the following hardening parameters: core box tempera-
ture, 250 °C; time of being in a core box, 45–120 seconds; binder addition, 2.8%).
Thermogravimetric tests of this new binder indicate that the temperature initiating
its decomposition and burning is nearly the same as of phenol resin in the shell
process, but the decomposition rate is much higher. This binder is highly ecological,
since during its thermal decomposition the emitted gases contain mainly: CO2, ace-
tic acid, and furfural (burned sugar). Traces of harmful elements were not found.
Unpleasant odors were also eliminated both at a molding sand preparation stage and
during a mold pouring with liquid metal. Thus, this technology is environment-
friendly [86, 88–91].
13.9 Synthetic Polymer-Based Composite Binders
Polylactide (PLA)- or Polycaprolactone (PCL)-Based Composite Binders

Studies on utilizing as binder additions – apart from natural polymers – synthetic
biodegradable polymers originated from renewable sources are carried out. These
binder additions allow for a certain reduction of binder components originated from
the crude oil processing. This has an essential influence on the harmfulness of the
given molding sand. Examples of synthetic polymers are polylactide or polylactic
acid (PLA) and polycaprolactone (PCL), which are polymers belonging to aliphatic
polyesters. They are completely biodegradable in a period from half a year to
13.9 Synthetic Polymer-Based Composite Binders 325
Fig. 13.13 Scheme manufacturing PLA as a polymerization result of lactide
CH3 O CH3
CH3
–H2O
OH O O
HO HO O
condensation
O O CH3 O
lactic acid low molecular weight prepolymer

Mw = 1000 - 5000
Fig. 13.14 Scheme manufacturing PLA by polycondensation lactic acid
Fig. 13.15 Lactic acid production on an industrial scale
Fig. 13.16 Preparation of polycaprolactone
2 years. They are obtained from renewable natural materials such as corn flour,
sugar beets, and potatoes. PLA is obtained as a polymerization result of lactide with
opening of a chain (ROP) (Fig. 13.13) or by polycondensation of lactic acid
(Fig. 13.14).
Lactic acid is obtained on an industrial scale during a catalytic addition of hydro-
gen cyanide to acetic aldehyde (Fig. 13.15).
Polycaprolactone (PLC) is obtained from caprolactone as a result of polymeriza-
tion with a chain opening (Fig. 13.16).
Properties of PLA and PLC depend on the chemical compositions of mers and
their placement along this polymer chain. The glass transition temperature of PLA
polymer equals app. 55 °C, of PCL polymer app. 60 °C, while the melting tempera-
ture of PLA equals app. 180 °C and of PCL app. 60 °C [92, 93]. On account of their
properties, especially a fast biodegradability, studies concerning the possibility of
using PLA and PCL polymers for molds and core production, have been undertaken
[94, 95]. These works are conducted in two directions: total elimination (Table 13.2)
(molding sand I) or only a partial substitution of the primary component (molding
sand II) of a binder (e.g., resin).
In case of the total substitution of up to now used binder by the synthetic polymer
a problem constitutes the development of a safe solvent for this polymer (molding
sand hardening occurs as a result of a solvent evaporation). Solvents proposed up to
the present are either carcinogenic (dichloromethane CH2Cl2) or inflammable (ace-
tone: CH3–O–CH3) [95]. For a molding sand with PLA as a binder the bending
strength of 1.8 MPa was obtained, while the mechanical reclamation ability of this
sand was better than of the sand with furan resin [95].
At a partial substitution (in amounts shown in Table 13.2, molding sand II) of
furan resin by PCL polymer, non-improvements of strength properties were found.
It can be only said, that the gases emissivity under a high-temperature influence
was lower.
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Part V
Environmental Aspects Mold and Core
Technologies
Chapter 14
Influence of the Technology of Molding
and Core Sands on the Environment
and Working Conditions: Summary
In order to assess each technology, including the molding and core sand technology,
in the aspect of its influence on the environment and work conditions, the analysis
of life cycles of all products should be performed. This analysis should start from
the raw materials output (sand, bentonite, coal) via the binders production (resins,
water glass) then the whole process of sands preparations and molds making, pour-
ing and cooling processes of molds, casting knocking out. The analysis should be
ended on the spent sand reclamation process and these sand utilization or storage
(Table 14.1). Only two elements of life cycles of molding and core sands, the most
important in consideration of their harmfulness, are taken into account in the hereby
paper. These are:
• Molding sand preparation process, making of molds and cores, mold pouring
with molten metals, mold cooling, and casting knocking out. This mainly con-
cerns gaseous substances released to the environment during these processes.
• Influence of spent molding and core sands, during their storage or recycling, on
the environment. The reclamation process, possibilities of utilization and storage
of after reclamation wastes. This concerns substances which could be eluted to
the environment.
14.1 E
mission of Harmful Substances from Molding
and Core Sands
This problem was presented in detail in previous chapters of this textbook, referring
to individual technologies. The emission into the air in foundry plans is not orga-
nized, it means it is difficult to detect and therefore it is hazardous for the environ-
ment and employees. The most important chemical compounds, which can be
released during the castings production of various alloys and molding sands with
different matrices and binding materials, were determined on the bases of numerous

334 14 Influence of the Technology of Molding and Core Sands on the Environment…
Table 14.1 List of substances identified in the air in cast iron and cast steel foundries during the
casting production
Substance Application or the emission source
Amines Preparation of urethane binders, thermal decomposition of
binders
Ammonia Thermal decomposition of hexamethylenetetramine,
decomposition of urea, and urethane binders
Bentonite Sands preparation, fire-resisting minerals
CO2 Burning of substances containing carbon (used for sands
preparation), melting in cupolas, fuels combustion in furnaces
and engines, CO2 applied as hardener in sands with water glass
Coal Coal dust, graphite, and carbon black used for making molds
and cores, coke for melting in cupolas, protective coatings for
molds and cores, electrodes in arc furnaces
Carbon monoxide Burning of substances containing carbon (used for sands
preparation), melting in cupolas, fuel combustion in furnaces
and engines, flame parting and welding
Chromite Chromite sand, fire-resistant materials
Chromium and chromium Alloy steels: melting, pouring, fettling, cutting, welding
oxides
Cristobalite Fire-resistant materials, high-temperature SiO2 modification
Fluorides Melting, slag forming material
Formaldehyde Phenol, urea and furan resins, thermal decomposition of
organic substances and making of castings
Furfuryl alcohol Furan resins
Aliphatic and aromatic Solvents of binder components, thermal decomposition of
hydrocarbons (e.g., benzene, organic substances, fuels
toluene, xylenes, naphthalene)
Hydrogen sulfide Wet slag granulation from melting processes and thermal
decomposition of sulfur compounds
Iron and ferric oxides Ferrous alloys: melting, pouring, cutting, fettling, welding
Isocyanate Urethane resins, thermal decomposition of urethane binders
Lead and its oxides Scrap melting
Magnesium and its oxide Spheroidal cast iron production
Manganese and its oxides Ferrous alloys: melting, pouring, cutting, fettling and welding
Nickel and its oxides Alloy steels: melting, pouring, cutting, fettling and welding
Nitrogen oxides Thermal decomposition of urea and urethane binders, burner
cutting, welding
Olivine Olivine sand, fire-resistant materials
Phenols (e.g., phenol, cresol, Phenol binders, thermal decomposition of organic substances
xylenol) contained in sands
Polycyclic aromatic Coal-tar pitch, thermal decomposition of substances containing
hydrocarbons (PAH) coal, fuel combustion in furnaces and engines
Silica High-silica sand, fire-resistant materials, casting shot blasting.
Sulfur dioxide Combustion of fuels containing sulfur, molding sands
hardening by means of SO2, thermal decomposition of furan
resins
(continued)
14.1 Emission of Harmful Substances from Molding and Core Sands 335
Substance Application or the emission source
Tridymite Fire-resistant materials, high-temperature quartz form
Vanadium and its oxides Alloy steels
Zinc and its oxide Melting of galvanized scrap
Calcium carbide Melting, slag components, desulfurizing
Other contaminations of the air
Acrolein Thermal decomposition of vegetable oils
Alcohols (e.g., isopropyl) Solvent of binder components, component of urea resins,
solvent of protective coatings of molds and cores
Cadmium and its oxide Melting of alloys
Calcium carbonate, calcium Melting, slag components, desulfurizing, dephosphorization
carbide, calcium oxide
Carbon disulfide CS2 Decomposition of furan resins hardened by sulfonic acid
Carbonyl sulfide COS Decomposition of furan resins hardened by sulfonic acid
Copper and its oxides Scrap melting, arc grooving by means of electrodes covered by
coal
Cyanides (e.g., hydrogen Thermal decomposition of urea and urethane binders, heat
cyanide) treatment of special castings
Esters ALPHASET process, solvents
Ethyl silicate Silicate binders
Ferroalloys Melting and casting
Methyl ethyl ketone peroxide Molding sand hardening process, by means of SO2
Nitrogen heterocyclic Coal-tar pitch, thermal decomposition of molding sands
compounds (e.g., pyridine) containing coal
Nitrosamines They are formed in molding sands by reactions of nitrogen
oxides with amines
Heterocyclic oxygen Furan resins
compounds (e.g., furan,
methylfuran)
Ozone Welding in inert gas
Phosphoric acid (V) Catalyst for furan resins
Phosphine PH3 Reaction of water with phosphides contained in ferroalloys,
decomposition of furan resins, furan resins hardened by
phosphorous acid
Radon Zirconium sand
Sulfonic acids Catalyst for furan resins
Heterocyclic sulfur compounds Decomposition of furan resins
(e.g., thiophene)
Talc Protective coatings of molds and cores
references and own investigations. During molds and cores productions such dan-
gerous substances, e.g., carbon monoxide, formaldehyde, phenol, furfuryl alcohol,
isocyanides, and amines, can be formed. The attention should be directed to the
significant number of substances from the HAPs group since a lot of them are car-
cinogenic or mutagenic. Apart from standard organic substances, which can be gen-
erated under the temperature influence at the determined chemical composition,
substances from the PAH group or dioxanes and furans can be expected in
waste gases.
The example of highly harmful molding sands, especially at the stage of the
mold pouring with molten metal, are sands with bentonite and with additions of
substances containing carbon, able to form lustrous carbon. Molding sands with
bentonite, without coal dusts, belong to environment friendly sands (all components
are of a natural origin). However, the introduction of coal dusts into this sand causes
that it becomes the most dangerous for the environment (Table 14.2). When such
mold is poured with molten metal the additions containing coal are decomposed and
toxic gases are emitted: NH3, H2S, PH3, benzene derivatives, PAHs, and BTEX,
including highly carcinogenic benzo(a)piren. A part of these substances is released
into the environment directly after the mold pouring with molten alloy and another
part is condensing on matrix grains. This part after successive cycles of sand circu-
lations and after repeated mold pouring with molten metal is also released into the
environment. In several castings made in sands with bentonite, the application of
cores is necessary. These cores are the most often made by the cold-box, hot-box, or
coated sands technologies, which cause additional emissions of gases. During cast-
ing knocking out the burned molding sand with bentonite is mixed with the burned
core sand, and such mixture is subjected to the reclamation. Thus, the remains from
organic binders and not active bentonite are transferred to the reclaim, worsening its
quality. This is especially disadvantageous when the molding sand is only subjected
to a partial reclamation, which encompasses the removal of dusts and improvement
of the grain distribution of the return molding sand.
Therefore investigations concerning molding sands with bentonite are mainly
focused on the development of such substitutes of sea coal, which would produce
the same technological effect and be less harmful for the environment.
Since the majority of castings are produced in molds on high-silica sand matri-
ces, the special attention should be directed to the air contamination by crystalline
Table 14.2 Harmfulness of molding sands produced by various technologies

Dust emission PAHs emission Benzo(a)pyrene
Kind of molding sands (mg) (mg) emission (mg)
Green sand 1.625 1.021 1.20
Molding sands with phenol- 0.023 0.007 0.07
formaldehyde resin
Molding sands with furan resin 0.050 0.010 0.012
Shell sand 0.157 0.107 0.021
Silicate ester 0.017 0.013 0.010
14.1 Emission of Harmful Substances from Molding and Core Sands 337
respirable silica (SiO2 particles of dimensions at least 100 times smaller than sand
grains). Potential sources of the exposition to the respirable silica influence in the
foundry plant are transport of fresh sands and the reclaim, cores forming and pro-
duction, casting knocking out and their treatment, and reclamation of spent sands.
The presence of respirable silica in the air increases the risk of serious illnesses such
as pneumoconiosis, lung cancer, and kidney sicknesses.
14.2 I nfluence of Spent Molding and Core Sands

on the Environment
In the foundry plant, which has the installation for the reclamation, sand grains are
circulating and used several times. Mechanical rubbing processes during the prepa-
ration of molds and during the mechanical reclamation, an exposure to thermal
shocks and high temperatures, are causing that sand grains are cracking and break-
ing, which changes their shape and makes them useless in the foundry plant. When
sand losses its properties and is not suitable for production of molds and cores, it is
removed from the foundry plant and treated as waste materials (Spent Foundry
Sand – SFS). Main factors deciding on the SFS properties are the alloy kind, cast-
ing process, and applied molding sand technology. Several possibilities of using
the SFS can be found in references. The SFS can be useful, among others, in civil
engineering. Together with fly ash, it can be used in production of blocks for build-
ing walls, for the production of fire-resistant mortars or bricks [3–6]. The SFS
constitutes a good material for foundations and for lower bases at building high-
ways [7]. A wide zone of the waste management is the highway engineering and
cement industry, where it substitutes natural aggregates at the production of cement
asphalt, concrete, pitchers or has other applications [8, 9]. Foundry plants have a
serious problem with the waste sand management. Partially this is an effect of clas-
sifying such sands – in several countries – as dangerous wastes, which consider-
ably increases storage costs. These costs in the USA equaled 34 U$/Mg and in
Great Britain 4.3 U$/Mg [10]. However, in such countries as Brazil, Portugal, and
European countries, these waste sands are treated as inert wastes and classified as
not dangerous. Only a part of spent molding sands is subjected to the reclamation
process and the obtained reclaim is used in the production of molding sands. A
significant part of the SFS must be managed outside foundry plants. A majority of
these wastes is stored in municipal or private storage yards as not dangerous wastes
[11]. Annually 10–15 million Mg of SFS are generated in the USA. Only 2% of
these wastes are considered to be dangerous. Only 2.6 million Mg of these wastes
is advantageously managed outside the foundry plant, out of which 14%, for soil
enrichments [7, 12]. There are several possibilities of the waste sand management
outside foundry plants. However, such wastes must satisfy the determined require-
ments concerning their composition, contents of hazardous organic substances
(which can be eluted), contents of heavy metals, coarseness, ability of water
absorption, etc. In the case of spent sands, their harmfulness can be assessed by the
contents of dangerous substances or by – more important for the environment –
their inclination for elution. Main fields of a useful management of spent molding
and core sands are the soil production, building of river embankments, or using
sands with bentonite for removal of zinc and trichloroethylene from sewages [13].
The reclamation of spent sands becomes the need in the majority of foundry plants,
due to increasing transport costs and raw materials prices. A foundry plant manage-
ment can chose either to store spent sands, pay for fresh sands and their transport
to the plant, pay for transport of spent sands and pay for their storage or to apply
the reclamation. In case of the mechanical reclamation costs are much lower and
contain electrical energy costs, buying and transporting of much smaller amounts
of fresh sands (up to 10%), and disposal of 5–10% of after reclamation dusts, with
taking into account that these dusts can be classified as dangerous. An additional
advantage for the environment constitutes a lower emission of combustion gases
since the transport is significantly limited. Three basic reclamation methods are
applied: dry method (mechanical), wet method, and thermal method. Each of them
influences the environment in a slightly different way. The profitability of the rec-
lamation process depends, to a significant degree, on its efficiency (amount of the
removed binder in relation to the amount remaining in the reclaim) and on its influ-
ence on shapes and sizes of the reclaimed grains [14–16]. The SFS must be prop-
erly prepared for each reclamation method (selection of granulation, pH value,
organic substances presence, kind of sand). Physical–chemical characteristic and
chemical composition of the SFS should be investigated to protect humans and
nature against their negative influences. The important assessment element of each
technology is the evaluation of final products, i.e., reclaims and dusts from the
mechanical reclamation process, gases released in the thermal reclamation process
and sewages from the wet reclamation process. The fact, that in case of molding
sands with organic binders, which are subjected to thermal decomposition after the
mechanical reclamation, certain amounts of not burned or weakly burned but hard-
ened binder remain in the reclaim should be taken into account. This binder will be
decomposing in the next cycle, thus causing an increase of liberated gases.
Therefore molding sands, which will allow to produce good castings at the minimal
negative influence on the environment, are intensely looked for. The example can
be the molding sand with water glass hardened by physical factors, e.g., by drying.
Another group of such molding sands constitute hybrid sands, which are mixtures
of inorganic components with organic ones, e.g., resin modified by bentonite
nanoparticles or water glass with collagen additions [17–19]. Apart from standard
organic compounds, which can be formed under an influence of a temperature,
substances from the PAH group or dioxins and furans (Table 14.3 [21]) can be
expected. The basic test, for the assessment of the possibility of utilizing the SFS,
is the elution test, performed according to the proper procedure. One of such tests
is the Toxicity Characteristic Leaching Procedure (TCLP) developed by the
Environmental Protection Agency (US EPA) [20], used for evaluating whether the
given waste has toxic properties and can be dangerous. Since waste sands are usu-
ally mixtures of sands of various composition, originated from various technolo-
14.2 Influence of Spent Molding and Core Sands on the Environment 339
Table 14.3 The chemically analysed PAH compounds in spent foundry sands (mg kg−1)
Sands type, mg kg−1
Furan/acid Silicate
Green sands sands Phenolic/ester sands sands
Sample number 1 2 3 4 5 6 7 8 9 10 11
Naphthalene 2.50 8.30 6.00 0.06 0.19 0.07 0.49 0.84 0.55 0.67 0.05
2-Metheylnaphthalene 1.40 6.30 2.40 0.04 0.01 0.01 0.15 0.21 0.12 0.14 0.03
1-Metheylnaphthalene 0.86 5.60 1.17 0.02 0.03 0.01 0.02 0.11 0.07 0.07 0.01
Biphenyl 0.88 1.60 1.00 0.06 0.10 0.09 0.18 0.28 0.13 0.17 0.02
3-Methylbiphenyl 0.19 1.10 0.37 0.00 0.09 0.01 0.02 0.09 0.03 0.05 0.01
Acenaphthylene 0.05 0.16 0.07 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00
Acenaphthene 0.23 0.31 0.08 0.03 0.04 0.01 0.01 0.02 0.01 0.04 0.00
Dibenzofuran 0.44 1.00 0.48 0.00 0.09 0.02 0.16 0.38 0.13 0.21 0.02
Fluorene 0.14 0.34 0.33 0.00 0.06 0.00 0.02 0.07 0.02 0.21 0.01
Dibenzothiophene 0.05 0.05 0.07 0.00 0.00 0.01 0.00 0.01 0.00 0.02 0.00
Phenanthrene 0.82 1.30 1.10 0.00 0.04 0.01 0.04 0.08 0.07 0.00 0.07
Anthracene 0.16 0.22 0.34 0.00 0.01 0.00 0.03 0.11 0.03 0.17 0.02
2-Methylanthrasene 0.25 0.47 0.47 0.00 0.01 0.00 0.11 0.14 0.03 0.07 0.02
1-Methylanthrasene 0.21 0.33 0.30 0.00 0.00 0.00 0.00 0.02 0.00 0.05 0.02
2-Phenylnaphthalene 0.16 0.14 0.87 0.00 0.01 0.00 0.02 0.02 0.02 0.01 0.02
Fluoranthene 0.14 0.30 0.31 0.01 0.00 0.00 0.01 0.03 0.01 0.06 0.02
Pyrene 0.10 0.22 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.03 0.02
gies, the elution tests must be performed relatively often. All samples of molding
sands, regardless of their technology and the casting alloy grade, contained sub-
stances from this group. The total concentration of these substances was changing
in dependence of the kind of alloy and sand, but naphthalene constituted approxi-
mately 30% in each sand. Each substance from the PAH group had a higher con-
centration in spent molding sands with bentonite, than in spent sands with
chemically hardened binders. Out of all molding sands with chemically bound
binders, the PAHs concentration in sands with acid hardened furan resin and in
sands with water glass hardened by CO2 were lower than in phenol molding sands
hardened by esters. The kind of alloy poured into the mold has a significant influ-
ence on the amount of substances from the PAH group. Concentrations of these
substances in molding sands were in the following order: cast iron > aluminum
alloys > cast steel. High concentrations of substances from the PAH group in mold-
ing sands with bentonite is the effect of using organic additions for improving
properties (e.g., substances generating lustrous carbon) and cores made of sands
with furan or phenol resins. In addition, the molding sand with bentonite circulates
in cycles a few times which causes that these substances are cumulating in the sand.
Dungan R.S et al. tested the SFS for the contents of polychlorinated dibenzodi-
oxins PCDD, polychlorinated dibenzofurans (PCDF), and polychlorinated biphe-
nyls (PCB), with regard to the possibility of utilizing these sands in the agriculture
[22, 23]. Analyzing 10 various spent sands, originated from cast iron, cast steel and
aluminum alloys foundries, it means molding sands with bentonite, shell sands, and
molding sands with phenol-urethane binders hardened in the ambient temperature,
they stated that – admittedly – there were conditions to generate these substances,
and they could be found in spent foundry sands, but their concentrations were at the
lower limit of the soil requirements. Since molding sands components are minerals
the origin of PCDD, PCDF, and PCB can be natural or anthropogenic. It is not pos-
sible to exclude totally the formation of PCDD and PCDF during the casting pro-
duction process, though it is unlikely due to small contents of chlorine and organic
carbon in these sands. Metals from spent molding sands are leaching in a very low
degree only, except of metals being components of casting alloys. The elution
degree of some metals depends, among others on pH of the solution, e.g., the elution
degree of Cr from molding sand with furan resin increases when pH value increases
[21, 24–26]. Miguel R.E. et al. investigating metal elution from the SFS originated
from various technologies and obtained from mold poured by cast iron or liquid
steel, found in the filtrate the highest concentrations of such metals as Al, Ba, Fe,
Mg, Mn, and Zn. In addition to which, the contents of metals in molding sands was
increasing after each reclamation cycle [7, 27]. The obtained values of metals elu-
tion from spent molding or core sands are compared with allowable values of these
metals concentration in underground waters. The temperature of molten metals
poured into molds is the most important parameter having the influence on the for-
mation of substances, in molding sands with chemically bound binders and – in
consequence – subjected to elution. Compositions of eluates obtained from the SFS
are given in Table 14.4. Molding sand 1 originated from the mold poured with Al
alloy of a temperature of 730 °C, while molding sand 2 originated from the mold
poured with cast iron of a temperature of 1400 °C [28]. Molds were made of mold-
ing sands with furfuryl-urea resin containing below 25% of furfuryl alcohol. This
resin was hardened by p-toluenesulfonic acid with 1% addition of sulfuric acid. The
elution test of spent sands was performed according to the Polish standard: PN-EN
12457-4:2006. In addition, the obtained results were compared with the require-
ments of the TCLP test applied by US EPA (Table 14.4).
In water extracts obtained from spent molding sands, originated from molds in
which aluminum alloy castings were made, a small exceeding of nickel concentra-
tion, 0.515 mg/kg d.m. (allowable concentration equals 0.4 mg/kg d.m), and lead,
1.44 mg/kg d.m. (allowable concentration equals 0.5 mg/kg d.m.), were found. In
addition, there were some other excesses: dissolved organic carbon (DOC) 2220 mg/
kg d.m. (allowable concentration equals 500 mg/kg d.m.) and total dissolved solids
(TDS) 5180 mg/kg d.m. (allowable concentration equals 4000 mg/kg d.m.).
In water extracts obtained from spent molding sands, originated from molds in
which cast iron castings were made – in relation to requirements of storage yards for
inert wastes – the concentration exceeding occurred for zinc (4.3 mg /kg d.m. while
allowable equals 4 mg/kg d.m.) and for dissolved organic carbon (1600 mg/kg d.m.
14.2 Influence of Spent Molding and Core Sands on the Environment 341
Table 14.4 Investigation results of the elution of spent molding sands originated from mold
poured with Al alloy (T = 730 °C) (Sample 1) and cast iron (T = 1400 °C) (Sample 2) as well as the
limit elution values, determined for wastes other than dangerous and inert, which are not municipal
wastes, allowed to be stored in storage yards for wastes different from dangerous and inert wastes
and for inert wastes (mg/kg of d.m.)
The limit
elution
values, Maximum
Sample 1 determined The limit concentration
from mold for wastes elution of wastes
poured Sample 2 different values determining the
with Al from mold from determined toxic nature of
alloy poured with dangerous for wastes the waste
T = 730 °C iron alloy and inert from inert according to
mg/kg) T = 1400 °C wastes wastes, the test TCLP
No. Component d.m. mg/kg) d.m. mg/kg d.m. mg/kg d.m. mg/dm3
1 Arsenic < 0.010 0.018 2 0.5 5.0
2 Bar 0.290 1.84 100 20 1000
3 Cadmium < 0.0050 0.029 1 0.04 1.0
4 Total chromium 0.066 <0.030 10 0.5 5.0
5 Copper 1.95 0.143 50 2 25
6 Mercury <0.005 <0.005 0.2 0.01 0.2
7 Molybdenum <0.040 <0.040 10 0.5
8 Nickel 0.515 0.361 10 0.4 20
9 Lead 1.44 0.150 10 0.5 5.0
10 Antimony <0.010 <0.010 0.7 0.06
11 Selenium <0.010 <0.010 0.5 0.1 1.0
12 Zinc <0.050 4.39 50 4 250
13 Chlorides <20 <20 15,000 800
14 Fluorides <1.0 <1.0 150 10
15 Sulfureous 110 51 20,000 1000
16 Dissolved 2220 1610 800 500
organic carbon
(DOC)
17 Solid dissolved 5180 3780 60,000 4000
substances
(TDS)
18 Total organic 7400 30,000
compounds
(TOC)
19 Benzene, 0.19 6 Benzene 0.5
toluene,
ethylbenzene,
xylenes
20 Polychlorinated <0.020 1
biphenyls
(PCB)
(continued)
The limit
elution
values, Maximum
Sample 1 determined The limit concentration
from mold for wastes elution of wastes
poured Sample 2 different values determining the
with Al from mold from determined toxic nature of
alloy poured with dangerous for wastes the waste
T = 730 °C iron alloy and inert from inert according to
mg/kg) T = 1400 °C wastes wastes, the test TCLP
No. Component d.m. mg/kg) d.m. mg/kg d.m. mg/kg d.m. mg/dm3
21 Mineral oil 9.17 500
C10–C40
22 Polycyclic 0.10 1
aromatic
hydrocarbons
(PAHs)
23 Phenolic index 0.31 1
d.m. dry matter
while allowable value equals 500 mg/kg d.m.). The relatively high zinc concentra-
tion in the eluate obtained from the SFS was the result of using galvanized scrap in
the metal charge (e.g., motor-car body sheets).
Spent molding sands with furan resin, hardened by acid, and originated from
molds, in which castings of aluminum alloys as well as of cast iron were made, were
fulfilling conditions of not being toxic. However, it should be taken into account that
in the TLCP test, a slightly different methodology is used and the elution conditions
are more demanding [29].
14.3 A
fter Reclamation Dusts and their Influence
on the Environment
The mechanical reclamation of spent molding sands is the method which found the
widest application, mainly due to economic and environment protection reasons.
This technology is utilized for molding sands with water glass and with organic
binders. As the result of this process, the basic product, i.e., the reclaim as well as the
by-product (waste), i.e., after reclamation dusts, is obtained. There is a simple depen-
dence: the smaller losses on ignition (LOI) indicate the reclaim the higher cleaning
degree of matrix grains. But in effect, more dusts are formed, at the same composi-
tion of the SFS subjected to the reclamation. These dusts contain significant amounts
of organic materials which make them dangerous wastes. It is assumed that – on the
average – the amount of after reclamation dusts from the reclamation of molding
sands with organic binders equals 5–10% of the initial amount of sands [30].
14.3 After Reclamation Dusts and their Influence on the Environment 343
The utilization or management problems of after reclamation dusts, originated

from the mechanical reclamation, have not been solved until now and it concerns
every foundry plant, which uses molding sands with chemically bound binders. On
account of significant contents of organic substances originated from binders, the
after reclamation dusts have the determined energetic value, which can be used as
the so-called waste heat. M. Holtzer et al. investigated the possibility of applying
these dusts as the energy source [31, 32]. To this aim, the prototype of the gas-fired
furnace into which the after reclamation dusts were blown in as a fuel was designed
and built [33].
The basic physical–chemical properties of after reclamation dusts, obtained at
the mechanical reclamation of various molding sands, are given in Table 14.5.
Marking of dust samples D1, molding sand bound by furan resin (matrix: high-
silica sand + chromite sand = 30:1); D2, molding sand bound by furan resin (matrix:
90% of reclaim +10% of fresh high-silica sand); D3, molding sand bound by furan
resin (matrix: high-silica sand); D4, molding sand bound by phenol resin hardened
by esters (matrix: 60% of reclaim +40% of fresh high-silica sand); D5, molding
sand bound by alkyd resin (matrix: high-silica sand + chromite sand = 5.7:1); D6,
molding sand bound by alkaline phenol resin hardened by esters (matrix: 60% of
reclaim +40% of fresh high-silica sand).
Energetic properties of after reclamation dusts and the technical analysis of these
dusts are shown in Table 14.6 [34].
After reclamation dusts originated from the mechanical reclamation of molding
sands with various resins often differ in their physical–chemical properties, chemi-
cal composition and energetic properties. This is mainly caused by the applied rec-
lamation system, its efficiency, the efficiency of the reclaim dedusting system and
the efficiency of separating the mixture of high-silica and chromite sands applied as
matrices. As high as possible, contents of combustible substances, it means carbon
compounds, are essential from the point of view of the possibility of utilizing the
energy contained in after reclamation dusts either in the process of individual burn-
ing (e.g., in gas-fired furnaces) or in joint burning with carbon carriers (e.g., sea
coal, brown coal, etc.). The calorific value of dusts is tightly related to the carbon
content. The highest calorific value had dust D2; it was above 13 MJ/kg of dust.
Table 14.5 Basic properties of the after reclamation dusts originated from the mechanical
reclamation of molding sands with various chemically bound binders
Marking of dust
Specified dust parameter D1 D2 D3 D4 D5 D6
pH 5.02 5.52 4.30 10.20 9.01 10.41
Humidity (%) 1.6 3.1 2.5 1.30 1.15 2.26
Electrolytic conductivity (mS) 4.12 8.82 4.51 7.35 0.84 6.24
Loss on ignition (in 950 °C) (%) 20.30 46.00 29.20 5.50 22.17 3.59
Surface area (cm2/g) 6927 10403 10143 6037 9243 18998
Table 14.6 Energetic properties and the technical analysis of dusts from the mechanical
reclamation process of molding sands with resins (marking of dusts the same as in Table 14.5)
Marking of after reclamation dust
Determined property, symbol, metric unit D1 D2 D3 D4 D5 D6
Residue of combustion content, Aa(%) 80.3 55.2 71.3 93.9 77.4 96.7
Volatile matter content, Va (%) 6.92 12.50 9.94 3,70 7.82 2.06
5004 13,746 7108 1382 6769 1209
Heat of combustion, Qsa (J/g)
4838 13,439 6884 1304 6589 1132
Calorific value, Qia (J/g)
0.81 1.94 1.13 0.04 0.02 0.01
Total sulfur content, Sta (%)
0.16 0.35 0.06 0.04 0.02 0.01
Sulfur content in the residue of combustion, S Aa (%)
0.65 1.59 1.07 0.00 0.00 0.00
Combustible sulfur content, SCa (%)
14.7 35.3 20.1 4.0 18.4 1.1
Content of carbon, Cta (%)
0.65 1.16 0.86 0.29 0.77 0.14
Content of hydrogen, H ta (%)
Content of nitrogen, Na (%) 0.09 0.46 0.80 0.08 0.77 0.02
This dust, apart from a higher carbon content, was characterized by the highest
contents of combustible hydrogen, which influences the calorific value. When the
after reclamation dusts are to be stored or utilized apart the foundry industry, per-
forming of the elution test is necessary. These tests indicated that in the case of dusts
originated from the mechanical reclamation of molding sands with furan resin, only
three parameters do not meet the criteria allowing to store these dusts in storage
yards for inert wastes. These are too low pH, too high contents of dissolved organic
carbon (DOC) and too high contents of total dissolved substances (TDS). Moreover,
total organic carbon is – in practice – dissolved organic carbon, that is why its con-
tents is so high [7, 12]. The pH value can be easily increased, since often the cores
with resins of alkaline character are applied as binders in molds of molding sands
with furfuryl resins. Dusts originated from the reclamation of molding sands of
various chemical characters will have, for sure, pH ≥ 6, which meets the require-
ments for storage yards for inert wastes. Taking into account relatively high calorific
values of certain dusts (D2), it should be expected that the efficient method of their
utilization will be burning, e.g., in gas-flux (for initiating and later – when needed –
for sustaining burning) or co-burning with solid carbon carriers (e.g., sea coal or
brown coal) [32]. Attempts to utilize these dusts as additions to building products
were made [31].
References 345
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Index
A Alkaline phenolic methyl formate hardened

Abnormal temperature, 250 (BETASET), 198–200
Acid amides, 57, 58 Alkaline sands, 198
Acid demand value (ADV), 114 Alkanes, 18, 19, 23
Acidic environment, 90 Alkenes, 23–25
Acidic salts, 213 Alkyd resins
Activators, 221 cobalt salts, 83
Active coatings, 286 fatty acids/vegetable oils, 83
Addition reaction, 16 polyester, 83
Advanced oxidation process (AOP), 268 polymerization, 84
Aerobic biodegradation, 75 properties, 84
Aggravating regulations, 220 structure, 84
Air emission sources, 141 Alkyl groups
Alcohol-based coatings, 287 aliphatic hydrocarbons, 20
cost reduction, 287 aromatic hydrocarbons, 21, 22
isopropyl alcohol, 286 unsaturated aliphatic hydrocarbons, 20
water, 292 Alkynes, 25–27
Alcohols ALPHASET process
acidic properties, 44 alkaline metals, 173
aliphatic alcohols, 36, 42, 43 alkaline salts, 172, 173
aromatic alcohols, 36, 43 environment and work conditions, 175–177
chemical properties, 42 ester selection, 174
properties, 44 mechanical and thermal reclamation, 174
Aldehyde group, 46 phenol–formaldehyde resin
Aldehydes and ketones ester, 172
aldehyde group, 46 hardening mechanism, 169–171
carbonyl group, 46, 47 polymerization products, 168
hydrogenation, 48 properties, 169
oxidation, 47 reclamation process, 171–172
properties, 47 small and medium castings, 168
Aliphatic alcohols, 36, 42, 43 water addition, 174–175
Aliphatic aldehydes, 86 ALPHASET technology, 122
Aliphatic amines, 56, 57 Aluminosilicate coatings, 288
Aliphatic diisocyanates, 99 Aluminosilicate sands, 123, 124
Alkaline (Si–O–Na) groups, 221 Aluminum alloy castings, 210

Ecology, https://doi.org/10.1007/978-3-030-53210-9
348 Index
Aluminum castings, 210 VOC emission, 192

Aluminum sulfate, 213 work environment, 196, 198
Amber, 81 Amine resins, 84
Amine hardened phenolic–urethane Amino plastics, 63
cold-box (PUCB) Amorphous, 91
advantages, 186 Amorphous carbon (AC), 257
application, 186, 193, 195 Amylase, 80, 266
applied solvents, 187 Amylopectin, 266
aromatic hydrocarbons, 193 Anaerobic biodegradation, 75
atmosphere character, 196 Anionic polymerization, 69
binder fraction, 188 Arene, 30
BTEX emission, 194–196 Aromatic alcohols, 36, 43
carrier gas, 188 Aromatic amines, 57
catalysts, 189 Aromatic diisocyanates, 98, 99
components, 187, 189 Aromatic hydrocarbons, 193
core-making machine, 188 Aromatic solvents, 192
development, 192, 193 Aromatic sulfonic acids, 103
DMEA, 191, 192 Aromatization
DMIPA amine, 191 bond structure, 30
drawbacks, 191 BTEX group, 34, 35
ESHAMINE plus process, 191 character, 31
gases emission, 194 common and IUPAC names, 30
gassing, 191 electrophilic substitution, 32, 33
harmful substances, 193 liquids/solids, 33
hazardous substances, 192 oxidation, 33
hydrous protective coatings, 188 PAHs, 36–41
inter-grain spaces, 192 quasi-unsaturated compounds, 30
isocyanate group, 188 structural isomers, 31
less reactive amine, 191 Ashland’s phenol process, 188
more reactive amine, 191 Atomic bonds, 16
odor emissions, 194, 195 AWB® technology, 234
organic acid chlorides, 187
PAH emission, 195, 197
phases, 192 B
polar solvents, 187 Bentonite, 246, 254
polyisocyanate, 188, 190 absorption properties, 245
polyurethane binder, 188, 190 binding properties, 246
polyurethane molecules, 191 bonding bridges, 251
process cold-box plus, 191 CEC, 249
process efficiency, 191 cis- and trans isomers in octahedral
properties, 189, 190 structure, 247
resin, 188 component, 246
room temperature, 188 composition, 246, 247
silica–organic solvents, 193, 194 deactivation temperature, 249, 250, 258
structural formulae, 187 dehydration process, 250
structure, 195 inter-packet spaces, 247
TEA, 189, 192 ionic capacity, 249
TEOS-based binder, 193 MMT, 246–251
tertiary amines, 187 modification, 245, 251
TGA/DSC/MS technique, 196 molding sands, 243
thermal decomposition mechanism, 196 natural calcium, 248, 249
TMA, 188 octahedral layer, 246, 247
toluene diisocyanates, 188, 189 optimal quality, 255
Index 349
properties, 249 Cast iron, 267

reclamation of molding sands, 263, 264 Cast steel, 9
soda-activated, 248 Casting Emissions Reduction Program
sodium, 248, 249, 251 (CERP), 3
swells, 246 Casting materials
technological requirements, 251 classification, 113
tetrahedral layer, 246, 247 Cation exchange capacity (CEC), 249
Wyoming bentonites, 248 Cationic polymerization, 69, 70
Bentonite clays, 246 Cellulose (fiber), 78, 79
Bentonite–water–sand matrix, 263 Cerabeads®, 125, 126
Benzene, 35 Chain growth, 67
alkyl derivatives, 33 Chain polymerization, 64–66
and aromatic compounds, 32 Chain transfer, 65
arene, 30 Chemical degradation, 78
homologues, 30 Chemical modification, 235
saturated hydrocarbon chains, 30 Chemical penetration, 289, 291
Benzene emissions, 270 Chemically cured polymers (duroplasts), 63
Benzene formation, 253 Chromite glaze, 123
Benzenesulfonic (BS), 103 Chromite sand, 122, 123, 201
Benzoyl and phenyl radicals, 66 cis-compounds, 24
Binder thermal destruction, 192 Cleantech process (Hüttenes-Albertus), 207
Binding materials, 5 Cleantech technology, 208
Binding molding sands, 287 Clear Air Act Amendments (CAAA), 2
Biodegradable polymers, 74, 75 CO2 hardened alkaline phenolic, 200–203
Biodegradation process, 78 CO2 system, 225–227
Biuret, 59 Coagulation threshold (CT), 225
Bound water, 250 Cobalt salts, 83
Brittle temperature, 63 Cold-box technology, 219
BTEX emission, 193–196, 202 Cold-setting processes
BTEX group, 34, 35, 253, 254, 267–269, alkyd oil, 178–180
271, 272 furan acid catalyzed (see Furan resins)
Burning, 252 no-bake (see No-bake process)
resol ester hardened (ALPHASET) (see
ALPHASET process)
C Colloidal solution, 224
Calcium montmorillonite (CaMMT), 248, 249 Colophony, 81
Calcium stearate, 213 Condensation polymers, 70–72
Carbon-based coatings, 286 Condensation resins, 87
Carbon dioxide, 219 Condensation zone, 258–260
Carbon sands, 126 Coordination polymerization, 71, 72
Carbon swelling effect, 254 CORDIS® technology, 232, 233
Carbonization process, 97 Core reinforcement, 213
Carbonyl group, 46, 47 Covalent bonds, 16
Carboxylic acids, 44, 49 Cresol, 254
characteristics, 48 Croning process (shell process), 212–214
chemical properties, 49, 52 Crystalline silica, 113, 118–120
derivatives, 52 Crystalloidal/colloidal, 223
dicarboxylic acids, 50 Cumene process, 85
esters, 52–55 Cumulated double bonds, 188
monocarboxylic acids, 50–51 Curing, 94
properties, 49 Cycloalkanes, 27–29
temperature, 49 Cycloalkenes, 29, 30
350 Index
D investment casting method, 309–314

Decarboxylation reaction, 49 Shaw’s method, 307–309
Degradable polymers fire-resisting coating, 302
biodegradable, 74, 75 FMP (see Full-mold process (FMP))
biodegradation process, 78 frozen molds, 316–318
chemical degradation, 78 FTIR and GC/MS analyses, 300
mechanical degradation, 77 full-mold method, 299
photochemical degradation, 77 gating and supplying systems, 300
photodegradable, 76 LFP (see Lost foam process (LFP))
physical factors, 76 main decomposition products, 300, 302
radiation/microorganisms/enzymes, 74 polymer
stored wastes, 74 collagen-based composite
thermal degradation, 76, 77 binders, 322–324
Dextrin, 255, 266 PLA and PCL, 324–326
Dibenzoyl peroxide, 67 polysaccharide, 324
Dicarboxylic acids, 50 α-starch-based binders, 321
Differential scanning calorimetry (DSC), 196 polymethyl methacrylate, 298
Diisocyanates, 100 polystyrene, 298
Dimethylethylamine (DMEA), 187, 189, 191, RP process (see Rapid Prototyping (RP)
192, 197 process)
Dimethylisopropylamine (DMIPA), 187, temperature, 297
191, 197 thermal decomposition, 299
Dimethylnaphthalene, 254 thermal degradation, 300, 301
Dimethylphenol, 254 V-Process (see Vacuum molding process
Dimethylpropylamine (DMPA), 197 (V-Process))
4,4′-Diphenylmethane diisocyanate Expanded polystyrene (EPS), 297
(MDI), 98, 100 Explosive penetration, 289
Dissolved organic carbon (DOC), 340, 344 External zone, 260
Double bond isomerism, 24
Dry oils, 205
Dry zone, 259 F
Fast recalculating matrix grain sizes, 127
Fats, 54, 55
E Fatty acids/vegetable oils, 83
Ecological technology, 264–266 Fayalite, 123, 254, 291
Electrophilic substitution, 32, 33 Fayalite Fe2SiO4, 285
Emission of gases, 279, 282 FeO oxide, 291
ENVIBOND technology, 271 Ferrous foundry particulate (FFP), 3
ESHAMINE plus process, 191 Ferrous oxide, 257
Esters Film-forming substances, 84
aliphatic and aromatic carboxylic acids, 53 Fine grains, 114
fats, 54, 55 Fire-resistant sol–gel coating, 291, 292
inorganic, 54 Flash pyrolysis, 96
irreversible basic hydrolysis, 53 Flask-less formation, 244
reaction of carboxylic acid, 53 Flow temperature, 64
reaction with ammonia, 54 Fluorine, 95
reversible acidic hydrolysis, 53 Formaldehyde, 214
waxes, 55 Formaldehyde (methanol/formic aldehyde)
Ethers, 45, 46 (HCHO/CH2O)
Ethyl urethane (NH2COOC2H5), 100 aliphatic aldehydes, 86
Ethylbenzene, 35 aqueous solutions, 86
Ethyltoluene, 254 classification, 86
Evaporative-pattern casting methods, 85
ceramic protective coats, 301 properties, 86
ceramic shell FOSECO, 233
Index 351
Foundry industry, 1 cast iron, 267

Free phenol, 90 green sands, 267, 272
Free radicals, 268 greenhouse gases, 267
Full-mold process (FMP), 297, 305–307 hydroxyl radicals, 268
Functional groups, 15, 17, 18 PAH group, 267
Furan resins reduction of emissions, 268
atmosphere changes, 151 Gas-hardened (cold-box) processes
binders, 146 advantages, 185
chain polymerization/polyaddition, 103 BETASET, 198–200
furfuryl alcohol, 101–105 catalyst, 185
furfuryl aldehyde (furfural), 101 chemical bases, 185
hardeners/catalysts, 146 CO2 hardened alkaline phenolic, 200–203
hardening process, 104 FRC, 202, 203
hardening rate, 148 HARDOX, 185, 186
harmful substances, 160–161 PUCB (see Amine hardened phenolic–
heating/chemical agents, 101 urethane cold-box (PUCB))
inorganic and organic acids, 103 Gassing, 252
modification, 104 GC/MS methods, 166
moisture presence, 151 GEOPOL® technology, 278, 279
polycondensation/condensation Geopolymer
polymerization), 103 advantageous, 277
polymerization process, 149 application, 277
raw materials, production, 101 binding character, 278
SMS (see Spent molding sands (SMS)) classification, 277
structure, 103, 104 concentrations of substances, 279
temperature, 147 GEOPOL® technology, 278, 279
thermal decomposition, 105, 149, 153–159 hardener influence, 277
water sources, 149 pollutants, 279, 280
Furan-urethane resin, 196 polymerization, 277
Furfuryl alcohol polymerization process, 277
environment protection, 103 polysialate, 277
linear oligomers, 103 structure, 277, 278
liquid polymer, 104, 105 volumes of gases, 279
monomers, 103 water glass, 278
plant materials, 101, 102 Glass temperature, 64
polymerization, 103 GMBOND™ technology, 139
production, 101, 102 Gradual polymerization, 64, 70–72
self-condensation reaction, 103 Grapes clusters, 257
structure, 104 Graphite, 268, 269, 271
water and organic solvents, 101 Greenhouse gases, 267
Furfuryl aldehyde (furfural), 101 Green sand molding, 130
Furfuryl resin, 210, 211 Green sands, 217
Fused silica, 125, 126 bentonite (see Bentonite)
castings of ferrous alloys, 244
chemically bound molding sands, 244
G clients requirements, 244
Gas evolution rates, 140, 142 flask-less formation, 244
Gaseous hydrocarbons, 19 gases emissions, 267–269
Gases emissions LCF (see Lustrous carbon (LC))
adsorption of aromatic substances, 268 machine forming technique, 244
alkyl radical, 269 manufacturing sand molds, 243
AOP, 268 properties, 244, 245
BTEX group, 267, 271, 272 raw materials, 243
352 Index
Green sands (cont) urea–furfuryl resin and catalyst, 210, 211

reclamation (see Reclamation of Hot-box/warm-box process, 217, 219
green sands) Hot coating, 212
substances, 273 Humid sand, 210
technology selection, 243 Hydrocarbon core, 15
thermophysical properties, 258, 259 Hydrocarbons, 253
water and role, 257, 258 alcohols, 36, 42, 43
aldehydes and ketones, 46–48
alkanes, 18, 19, 23
H alkenes, 23–25
Hazardous air pollutants (HAPs) alkynes, 25–27
concentrations, 254 aromatization (see Aromatization)
emission, 254, 271 atoms, 18
pyrolysis, 271 benzene (see Benzene)
Hazardous substances, 2 carboxylic acids, 48–55
Heat curing processes carboxylic Acids, 49
Croning process (Shell process), 212–214 cycloalkanes, 27–29
hot-box (see Hot-box technology) cycloalkenes, 29, 30
linseed oil oven bake, 205, 206 division, 18, 19
warm-box, 206–208 ethers, 45, 46
Helmholtz–Stern adsorption, 224 formulas, names and symbols, 18, 20–22
Helmholtz–Stern layer, 224 nitrogen organic compounds (see Nitrogen
Hexamethylenetetramine (HMTA), 90, organic compounds)
91, 210–214 phenols, 43, 44
Hexamine, 90, 95 sulfuric organic compounds, 61, 62
High-quality bentonites, 250 unsaturated, 18
High-silica sands, 201 Hydrogen cyanide (HCN), 77
Hot-box plus process, 210 Hydrous coatings, 210
Hot-box technology, 107, 206 Hydroxymethyl (−CH2OH) group, 88
acceleration, hardening process, 209 Hydroxymethylene and dimethylene ether, 93
advantages, 210, 211 Hydroxymethylene groups, 88
aluminum alloy castings, 210
aluminum castings, 210
bonding reaction, 209 I
catalyst, 209 Indicative exposure limit values, 6–8
catalyst fraction, 209 Innovatory sustainable technologies, 1
core making, 209 Inorganic binder
disadvantages, 211, 214 geopolymer, 277–279
environment, 211, 212 water-soluble cores, 279–282
furfuryl resin, 210, 211 Inorganic binder notion, 217
HMTA, 210 Inorganic binders, 280
humid sand, 210 Inorganic polymers, 72, 73
hydrous coatings, 210 Inorganic–organic and organic–metallic
iron castings, 210 polymers, 73, 74
mechanical properties, 208 INOTEC® technology, 230, 231
mixture, 209 Inter-grain spaces, 192
molding sand, 210 International Agency of Research on Cancer
PF novolak resin, 210 (IARC), 118
phenol–formaldehyde resin, 209 Ionic bonds, 15, 16
resins, 208 Ionic capacity, 249
shell-forming process, 208 Ionic polymerization, 68
steel castings, 210 Iron castings, 198, 210
thin cores, 209 Iron–chromium (Fe–Cr) slag, 124, 125
Index 353
Irreversible (chemical hardening) sodium Mechanical penetration, 289

silicate Mechanical reclamation method, 172
CO2 system, 225–227 Melting temperature, 64
organic ester system, 227–229 Metalcasting, 129, 277, 279–281
rheological properties, 228 Methyl ester of formic acid (HCOOCH3), 198
Irreversible basic hydrolysis, 53 Methyl formate, 198
Irreversible gelling reactions, 217 Methyl polymethacrylate (PMMA), 297–298
Isocyanates, 196, 197 Methylene bridge, 90, 210
Isopropyl alcohol, 286 Methylene glycol, 86, 87
Methyleneamine bridges, 91
Methylnaphthalene, 254
K Micelle model, 224
KCl, 281 Microwave heating, 219, 220
Kekule’s formula, 30 Mixed ethers, 45
Kerosene, 213 Mixture NaCl, 281
Kerphalite, 124 Modern casting houses, 134
Modification, sodium silicate
chemical, 235
L morphoactive organic compounds, 235
Lactic acid (LAc), 75 nanoparticles, 235–237
Linseed oil oven bake, 205, 206 physical, 234
Liquefaction, 252 ultrafine powders, 235
Liquid metal penetration, 289–291 zinc ferrite, 236, 238, 239
Liquid resol resins, 93 Modified polymers, 62
Lost foam process (LFP), 297, 302–305 Modified starch, 80, 81
Low-emission additives, 271 Mold casting processes, 129
Low-emission technologies, 269 Mold pouring, 201, 279
Lustrous carbon (LC) Molding and core sands, 133
advantageous, 269 bonding material, 130
AFS, 271 consumption, 138
coal dust (see Sea coal dusts) cores, 135
ENVIBOND binder, 271 destination, 131
formers and content of BTEX, 271, 272 ferrous castings, 129
graphite, 268, 269, 271 forming, 132
low-emission additives, 271 green sand molding, 130
low-emission technologies, 269 green sands, 134
mechanism hardening curve, 135
AC, 257 hardening process, 132
ferrous oxide, 257 polymers, 139
heterogenic nucleation, 257 production, 136
PC, 256, 257 self-setting sands, 135
primary pyrolysis, 256 technologies, 130, 131
secondary pyrolysis, 256 technologies applied in EU, 137
semi-coke represents, 257 Molding sands, 9, 131
thermal destruction processes, 256 advantages, 219
mixtures of bentonite+substance, 255, 256 average composition, 243
molding sand compactibility, 251 chemically bound, 244
S&B Industrial Minerals Company, 271 cold-box technology, 219
semi-technical conditions, 271, 272 drawback, 244, 278
environment-friendly, 219
greenness, 217
M hardening factor, 220
Magnesium oxide (MgO), 254 mechanical reclamation, 278
MDI-type isocyanate, 98 preparation, 201
Mechanical degradation, 77 properties, 187, 219
354 Index
Molding sands (cont.) Natural resins, 81

self-setting technology, 219 Natural rubber, 81
sodium silicate (see Sodium silicate) Neutral silane groups (Si–O–H), 221
technologies, 220 Nitriles, 60, 61
tensile strength, 220 Nitro compounds, 59, 60
water glass, 219 Nitrogen organic compounds
with inorganic binders, 217 acid amides, 57, 58
Molds pouring, 143 aliphatic amines, 56, 57
Monocarboxylic acids, 50–51 amines, 56
Monohydric alcohols, 42 aromatic amines, 57
Montmorillonite (MMT) nitriles, 60, 61
abnormal temperature, 250 nitro, 59, 60
aluminosilicate packets, 246 urea, 58, 59
bentonite clays, 246 No-bake process, 145, 178–180
bound water, 250 Non-ferrous metals, 122
calcium, 247–249 Non-ferrous metals alloys, 244
CEC coefficient, 249 Nonmetallic inclusions, 244
chemical composition, 248, 250 Normal/ideal temperature, 250
crystal structure, 246 Novolak resins, 87–92
hydrated aluminum hydrosilicate, 246 NOx, 77
individual, 247
ionic capacity, 249
large content, 260 O
low content, 260 Octahedral layer, 246, 247
mechanical properties, 251 Odor emissions, 194, 195
normal/ideal temperature, 250 Olivine sand
octahedral layers, 247 advantageous features, 122
sodium, 247–249 chemical composition, 121
structural water, 250 grain analysis, 122
structure, 247–249 high ADV, 121
swelling, 249 non-ferrous metals, 122
temperature influence, 250 reclamation system, 122
thermal resistance and binding One-stage resins, 93
properties, 246 Organic acid chlorides, 187
volcanic origin, 250 Organic binders, 273
Morphoactive organic compounds, 235 Organic chemical reactions
addition reaction, 16
elimination reaction, 16
N functional groups, 17, 18
Nanoparticles, 235–237 oxidation and reduction reactions, 16, 17
Naphthalene, 253 rearrangement reaction, 16
Natural calcium bentonites, 248, 249 substitution reaction, 16
Natural environment protection, 219 Organic chemistry
Natural fuels, 252 chemical reactions (see Organic chemical
Natural oils, 205 reactions)
Natural polymers (biopolymers), 62 compounds (see Organic Compounds)
cellulose (fiber), 78, 79 hydrocarbons (see Hydrocarbons)
division, 78 polymerization (see Polymerization)
modified starch, 80, 81 polymers (see Polymers)
natural resins, 81 Organic compounds
natural rubber, 81 bond types, 16
PLA, 81 classification, 17, 18
starch, 79, 80 nitrogen (see Nitrogen organic compounds)
Index 355
structure, 15 hydroxyl -OH group, 42

sulfuric, 61, 62 IUPAC system, 43
Organic ester system, 227–229 properties, 44
Organic metal compounds, 100 R–O–H particles, 44
Oxidizing toluene, 85 Phenol–urethane binder system, 97–100
Oxyanion, 200 Photochemical degradation, 77
Photochemical process, 67
Photodegradable polymers, 76
P Physical modification, 234
PAH emission, 195, 202, 203 Plasticizers, 84
Passive coatings, 286 Plastics, 62
Pattern instrumentation, 213 Polar solvents, 187
Penetration Polarized atomic bond, 16
liquid metal, 289–291 Poly(lactic acid) (PLA), 75, 81
Phenol–formaldehyde (PF) resins, 98, 208, Polyaddition, 70
209, 211 Polycaprolactone (PCL), 323–326
catalyst and molar ratio, 87 Polychlorinated biphenyls (PCB), 340
condensation resins, 87 Polychlorinated dibenzodioxines (PCDD),
methylene glycol, 86 273, 340
novolak resins, 89–92 Polychlorinated dibenzofuranes (PCDF),
polymerization, 87–89 273, 340
processing, 95 Polycondensation, 70
production, 86 Polycondensation process, 92
qualitative and quantitative Polycondensation reaction, 83, 87
composition, 95 Polycyclic aromatic hydrocarbons, 253
resol, 91–95 Polycyclic aromatic hydrocarbons (PAHs), 3,
substances, 95 36–41, 253–255, 267, 268, 271–273
thermal degradation, 95–97 Polyester resins, 83
thermo-hardened polymers, 87 Polyester thermoplastic resins, 83
Phenol/hydroxybenzene (C6H5OH) Polyhydric alcohols, 43
cresols and xylenols, 84 Polyisocyanate, 187, 188, 190
cumene process, 85 Polylactide/polylactic acid (PLA), 323–326
oral cavity and digestive tracts, 85 Polymerization
oxidizing toluene, 85 anionic, 69
properties, 85 cationic, 69, 70
weak acidic and weak basic properties, 85 chain, 64–66
Phenolic urethane (PU), 98 chain growth, 67
Phenolic–polyisocyanate binder, 260 coordination, 71, 72
Phenolic–urethane cold-box (PUCB) degree, 62
process, 98, 162 gradual, 64, 70–72
Phenolic–urethane no-bake (PUNB) initiation, 66–68
system, 98 ionic, 68
biourethane binder, 163 PF resins, 87–89
catalyst/self-setting, 162 photochemical process, 67
cold-hardened, 162 polyreaction, 65
environment influence, 164–167 radical, 66
urethane binder, 163–164 sodium silicate, 222
Phenol resin, 187 Polymers
Phenols, 43, 44, 254 amino plastics, 63
acidic properties, 44 chemically cured polymers (duroplasts), 63
and alcohols (see Alcohols) condensation, 70–72
carboxylic acids, 44 degradable, 74–78
chemical properties, 42 division, 63
356 Index
Polymers (cont.) metal gassing, 289

inorganic, 72, 73 molds and cores, 286
inorganic–organic and organic– nonmetallic inclusions, 289
metallic, 73, 74 passive coatings, 286
macromolecules, 62 properties, 287, 288
modified, 62 strengthening coatings, 286
monomers, 62 substitution, 289
natural, 62 (see Natural polymers surface active substances, 288
(biopolymers)) water (see Water-based coatings)
organic/inorganic macromolecules, 62 wet deposited coatings, 286
phase transformations, 63 p-toluenesulfonic acid, 103
phenol–formaldehyde resins, 63 Pyrolysis, 76, 252
physical structure, 63 Pyrolysis PF resin, 97
plastics, 62 Pyrolysis process, 257
properties, 64 Pyrolytic carbon (PC), 256, 257
secondary transformations, 63
synthetic, 62
thermoplastic, 63 Q
thermosetting, 63 Quartz sand, 113, 117, 118
Polyolefins, 76 Quickbond process, 251
Polyreaction, 65
Polysialate, 277
Polysiloxanes, 73 R
Polystyrene, 68, 77 Radical polymerization, 66
Polyurethane binder, 188, 190 Rapid Prototyping (RP) process, 318–320
Polyurethane chains, 192 Reactive silane Si–O–H groups, 222
Polyurethane molecules, 191 Reclamation/rebounding of green sands
Polyurethanes (PU), 94, 97, 98, 100 bentonite–water–sand matrix, 263
Polyvinylchloride, 76 chemically bound binders, 262
Porosity, 244 cold-box technology, 262
Process cold-box plus, 191 Croning’s technology, 262
Propylbenzene, 254 crushing, 260
Protective fire-resisting coatings dextrin, 266
active coatings, 286 distribution of devices, 260, 261
advantageous, 288 ecological technology, 264–266
alcohol (see Alcohol-based coatings) grinding and kneading, 263
aluminosilicate coatings, 288 maturing and aeration operations, 263
application, 285, 288, 289 mixing process, 262
benefits, 285 molding sand preparation, 260
binding molding sands, 287 molding sand rebounding, 260
buckles, 289 performing systematic tests, 263
carbon-based coatings, 286 phenolic–polyisocyanate binder, 260
casting quality, 285 properties, 262
coatings deposited and rebounding process, 260
dry substances, 286 sand character, 262
liquid form, 286 with bentonite, 263, 264
components, 287 Recrystallization process, 281
deposition, 291 Resins
fayalite Fe2SiO4, 285 alkyd (see Alkyd resins)
features, 286 application, 213
fire-resistant sol–gel coating, 291, 292 5th generation, 195
fire-resisting grain matrix, 287 formaldehyde (see Formaldehyde
function, 285 (methanol/formic aldehyde)
liquid metal penetration, 289–291 (HCHO/CH2O))
Index 357
furan resins (see Furan resins) Shooting molding sands, 191

hot-box technology, 208 Silica sand
natural, 81 application, 114
phenol, 84, 85 availability and low price, 113
phenol–urethane binder system, 97–100 casting defects, 115
urea–formaldehyde resins, 105–107 characterization, 115
Resistance to moisture, 277, 280, 282 chemical composition, 113, 114
Resol resins, 87, 88, 91–95 chemical properties, 114
Reversible (physical hardening) sodium FeO and MnO forming silicates, 114
silicate fine grains, 114
alkaline solution, 230 grain analysis, 117, 118
AWB® technology, 233, 234 grain size distribution, 114, 115
CORDIS® technology, 232, 233 melting point, 117
dehydration, 230 phase transformation, 117
higher and higher requirements, 229 phase transition, 118
INOTEC® technology, 230, 231 physicochemical properties, 114, 115
SOLOSIL TX process, 233, 234 polymorphous, 117
technologies, 230 segregation, 118
Reversible acidic hydrolysis, 53 steel castings, 114
thermal linear expansion characteristics,
115, 116
S thermal volumetric expansion
Salt cores, 280–282 characteristics, 115, 116
Sand division criterion, 133 Silica–organic solvents, 193, 194
Sand harmfulness, 10, 139 Silicate acid ester
Scabbing, 244 application, 194
Sea coal dusts Si-modified system, 193
ability of forming, 252 Slow pyrolysis, 96
application, 255 SO2 hardened epoxy/acrylic (free radical
benzene formation, 253 curing) (FRC), 202, 203
BTEX group, 253 SO2 hardened furan resins (HARDOX),
characteristics, 255 185, 186
excess and deficiency, 254 Soda-activated bentonite, 248
green sands, 252 Sodium bentonite, 248, 249, 251
hydrocarbons, 253 Sodium montmorillonite (NaMMT), 248, 249
MgO, 254 Sodium silicate
moisture gasification, 254 activation process, 221, 222
mold heating/pyrolysis, 252 alkaline (Si–O–Na) groups, 221
molten metal, 252 atmospheric conditions, 220
naphthalene, 254 colloidal solution, 224
oxidation atmosphere, 252, 253 condensation process, 222
oxidation reactions, 253 condensation reaction by dehydration, 221
polycyclic aromatic hydrocarbon condensation reaction process, 222
formation, 253 crystalloidal/colloidal, 223
pyrolysis, 252 deactivation reaction, 223
spheroidal cast iron, 254 decomposition reaction, 222, 223
substitutes, 254–256, 271 diffusion layer, 224
thermal decomposition, 252 free water, 224
Secondary transformations, 63 hardening process (see Water glass
Self-setting sands, 227 hardening process)
Self-setting technology, 219 Helmholtz–Stern adsorption, 224
Semi-industrial test, 202 Helmholtz–Stern layer, 224
Shell-forming process, 208 hot-box/warm-box process, 217, 219
358 Index
Sodium silicate (cont.) Thermophysical properties, green sands,

hydrolysis reaction, 221 258, 259
inorganic binders, 220, 221 Thermoplastic polymers, 63
micelle model, 224 Thermoplastic resin, 90
modification (see Modification, sodium Thermosetting polymers, 63
silicate) Thermostability, 95
module size, 225 Threshold limit value (TLV), 4
molecules adsorb, 224 Toluene, 35
natural environment protection, 219 Toluene -2,4-diisocyanate (TDI), 98, 100
neutral silane groups (Si–O–H), 221 Toluene diisocyanates, 188, 189
physical–chemical parameters, 219 Toluene emissions, 270
polymerization, 222 Toluenesulfonic (PTS), 103
preparation, 221 Total dissolved substances (TDS), 340, 344
reactive silane Si–O–H groups, 222 Toxicity Characteristic Leaching Procedure
structure, 221 (TCLP), 338
temperature, 221 trans-compounds, 24
tensile strength, 220 Transverse stone, 124
water solution, 221 Triethylamine (TEA), 92, 187, 189, 192, 197
with organic binders, 219 Trimethylamine (TMA), 187, 188, 197
zeta potential, 224 Trimethylbenzene, 254
SOLOSIL TX process, 233, 234 Trimethylphenol, 214
Spent Foundry Sand (SFS), 337, 338, 340 Trioxane, 48
Spent molding sands (SMS), 151, 152 Two-stage resins, 90
Spheroidal cast iron, 254
Spheroidal cast iron castings, 9
Starch, 79, 80, 255 U
Staurolite, 124 Ultrafine powders, 235
Steel castings, 210, 213, 291 Unsaturated fatty acids
Strengthening coatings, 286 structure, 205, 206
Structural water, 250 Unsaturated hydrocarbons, 18
Styrene, 66 Urea, 58, 59, 92, 94, 97, 101, 103, 104
Sulfuric organic compounds, 61, 62 Urea–formaldehyde resins, 105–107, 214
Symmetric ethers, 45 Urea–furfuryl resin
Synthetic polymers, 62, 76 properties, 210, 211
Synthetic sands Urethane, 97–100
carbon sands, 126
Cerabeads®, 125, 126
fused silica, 125, 126 V
Vacuum condition, 208, 264–266
Vacuum mixer, 264–266
T Vacuum molding process
TEOS-based binder, 193 (V-Process), 314–316
Terrestrial sands, 113 Vapor transportation zone, 259
Tertiary amines, 100, 187 Vegetable solvents, 193
Tetrahedral layer, 246, 247 Volatile organic compounds (VOCs), 3, 35
TGA analysis, 207
TGA/DSC/MS technique, 196
Thermal binder decomposition, 196, 200 W
Thermal decomposition, 96, 192, 272 Warm-box technology, 206–208
Thermal decomposition mechanism, 196 Warm coating, 213
Thermal degradation, 76, 77 Water-based coatings
PF resins, 95–97 advantages, 286
Thermogravimetric method, 154 alcohol, 292
Thermo-hardened polymers, 87, 98 disadvantages, 287
Index 359
molding sand technologies, 287 Wet deposited coatings, 286

stabilizing additives, 287 Work environment, 196, 198
Water glass, 278 Working conditions
activation process, 221 cast iron and cast steel, 334–335
application, 227 environment, 333, 337–342
and binders, 217 harmful substances, 333–337
bonding mechanism, 227 reclamation dusts, 342–344
coagulation process, 225 reclamation methods, 338
deactivation, 222 Workplace exposure limits (WELs), 5
esters, 227 Wyoming bentonites, 248
hardening process, 225
hydrated sodium acetate, 228
micelle forming, 223 X
modification, 235 Xylenes (o-xylene, m-xylene,
molding sands, 217, 219 p-xylene), 35
physical factors, 220 Xylenesulfonic acid (XSA), 103
polymerization, 235
properties, 224, 235
sand technologies, 219 (see also Sodium Y
silicate) Yellow dextrin, 266
solid/silicate binder, 221
Water glass hardening process
irreversible (chemical hardening), 225–229 Z
reversible (see Reversible (physical Zeta potential, 224
hardening) sodium silicate) Ziegler–Natty type, 72
sol coagulation, 225 Zinc ferrite, 236–239
Water-soluble alkaline phenol resin, 200 Zircon sand, 118, 121
Water-soluble cores, 279–282 Zirconium, 201, 213, 238

Mold and Core Sands in Metalcasting: Chemistry and Ecology: Mariusz Holtzer Angelika Kmita

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Mold and Core Sands in Metalcasting: Chemistry and Ecology: Mariusz Holtzer Angelika Kmita

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Mariusz Holtzer

Mold and Core Sands

Translated by Janina Pawlikowska-Czuba

ISBN 978-3-030-53209-3 ISBN 978-3-030-53210-9 (eBook)

© Springer Nature Switzerland AG 2020

Krakow, Poland, 08.2020 Mariusz Holtzer

IARC International Agency of Research on Cancer

TGA Thermogravimetric analysis

Part I Organic Chemistry

3 Synthetic Resins �������������������������������������������������������������������������������������� 83

Part II Organic Binder Systems of Molding and Core Sands

Part III Inorganic Binder Systems of Molding and Core Sands and

Part IV Special Technologies of Making Molds and Cores

13.8.3 Binder Based on Polysaccharide�������������������������������������� 324

Part V Environmental Aspects Mold and Core Technologies

Mariusz Holtzer Ph.D., is currently Full Professor at

Angelika Kmita is currently an Assistant Professor

Fig. 1.1 Sources of emission of compounds from the HAP group

Fig. 3.6 Condensation of hydroxyl derivatives���������������������������������������������� 89

Fig. 5.1 Fractions of green sand molding in technologies applied for

Fig. 6.11 Hydrolysis reaction of ester in a basic environment���������������������� 170

Fig. 9.3 Reaction of sodium silicate activation. (Adapted from

Fig. 13.1 Formation of polystyrene��������������������������������������������������������������� 298

Table 4.6 Chemical composition of typical olivine sand (mas.%)����������������� 121

Table 9.2 Parameters of cores made by various technologies������������������������ 233

Table 14.5 Basic properties of the after reclamation dusts originated

© Springer Nature Switzerland AG 2020 1

hazardous and dangerous chemical substances, air pollution, high temperatures,

Glutaraldehyde 111-30-8 0.4 0.6 – 0.05 0.2 0.05 0.2 Sen

WEL (Poland) TLV WELs (8) (G. Britan)

Crystalline silica 14,808- 0.1

40. Grochowalski A, Lassen C, Holtzer M, Sadowski M, Hudyma T (2007) Determination of

2.1 Organic Compounds: Structure and Bonding

Structure of Organic Compounds

© Springer Nature Switzerland AG 2020 15

2.2 Organic Chemical Reactions: Classifying

Classifying in Respect of Structural Changes

Table 2.1 Classification of organic compounds on the bases of functional groups

Sulfonic acid Sulfo-

Ester R-Oxycarbonyl- -an R

Nitrile Cyano- -nitrile

Alcohol −O − H Hydroksy-

Amine C − NH2 -amine

Classifying Based on Functional Groups

IUPAC – International Union of Pure and Applied Chemistry.

Fig. 2.1 Schematic division of hydrocarbons

Alkanes can be obtained by the thermal decomposition of carboxylic acid salts.

HC ≡ CH + Br2 → CHBr = CHBr

CHBr = CHBr + Br2 → CHBr2− CHBr2

1, 2 dibromoethene 1,1, 2, 2 tetrabromoethane

Reactions of alkanes with oxygen:

Propane CH2CH2CH3 Propylene group, (Pr)

Alkyl groups of unsaturated aliphatic hydrocarbons

CH3 Benzyl group

α-Phenyl (C6H5-phenyl group)

β-Phenyl (C6H5-phenyl group

Table 2.3 The alkanes homologous series

• Complete burning (Eq. 2.4):

CH 4 + 2O2 → CO2 + 2H 2 O + 890 kJ / mol (2.4)

2CH 4 + 3O2 → 2CO + 4H 2 O (2.5)

Table 2.4 The homologous C2H4 ethene C7H14 heptene

cis-but-2-ene trans-but-2-ene (2.7)

C2 H 4 + 3O2 = 2CO2 + 2H 2 O complete burning (2.11)

Krakow, Poland, 08.2020 Mariusz Holtzer

Part I Organic Chemistry

3 Synthetic Resins �� 83

Part II Organic Binder Systems of Molding and Core Sands

Part III Inorganic Binder Systems of Molding and Core Sands and

Part IV Special Technologies of Making Molds and Cores

13.8.3 Binder Based on Polysaccharide�� 324

Part V Environmental Aspects Mold and Core Technologies

Fig. 3.6 Condensation of hydroxyl derivatives�� 89

Fig. 6.11 Hydrolysis reaction of ester in a basic environment�� 170

Fig. 13.1 Formation of polystyrene�� 298

Table 4.6 Chemical composition of typical olivine sand (mas.%)�� 121

Table 9.2 Parameters of cores made by various technologies�� 233

2.1 Organic Compounds: Structure and Bonding

2.2 Organic Chemical Reactions: Classifying

2.3.6 Aromatization and Benzene

2.3.6.1 Aromatic Hydrocarbons from BTEX Group

2.3.6.2 Polycyclic Aromatic Hydrocarbons (PAHs)

2.4 Hydrocarbons with Functional Groups

2.4.1 Alcohols and Phenols

benzyl alcohol -phenylethyl alcohol -phenylethyl alcohol

2.4.3 Aldehydes and Ketones

2.4.4 Carboxylic Acids