Additives for High Performance Applications
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Preface xi
1 Analysis and Separation Techniques 1
1.1 High Performance Liquid Chromatography 1
1.1.1 Ionic Liquids as Mobile Phase Additives 1
1.1.2 Food Additives 12
1.1.3 Chaotropicity 14
1.1.4 Cigarette Additives 16
1.1.5 Chiral Separation 20
1.1.6 Peptides and Proteins 31
1.1.7 1,4-Dihydroxy-2-Naphthoic Acid 32
1.1.8 Diesel Lubricating Additives 32
1.1.9 Acidic Drugs 34
1.2 Chelation Ion Chromatography 39
1.3 Membranes 40
1.3.1 Carbon Dioxide Separation 40
1.3.2 Hollow Fiber Membranes 41
References 42
2 Electrical Applications 47
2.1 Capacitors 47
2.1.1 Triethanolamine 47
2.1.2 Supercapacitors 47
2.2 Electrokinetic Micropumps 50
2.3 Lead-Acid Batteries 50
2.3.1 Activated Carbon Additives 51
2.3.2 High Performance Positive Electrode 51
2.4 Lithium-Ion Batteries 53
2.4.1 Ionic Diffusion 56
2.4.2 Functional Electrolytes 56
2.4.3 Synergetic Effect of Conductive Additives 58
2.4.4 In-Situ Coating of Cathode by Electrolyte Additive 58
2.4.5 Bipolar Architectures 59
2.4.6 Janus Separator 63
2.4.7 Synthesis of Vanadium Cathodes 64
2.4.8 Graphite 64
2.4.9 Silicon 67
2.4.10 Carbon Nanotubes 69
2.4.11 Carbonate Additives 70
2.4.12 Borate Additives 73
2.4.13 Tris(pentafluorophenyl) Borane 78
2.4.14 Phosphoric Additives 79
2.4.15 Sulfur Additives 83
2.4.16 Isothiocyanates 90
2.4.17 Other Additive Types 92
2.5 Nickel Batteries 101
2.5.1 High-Rate Discharge Performance 106
2.5.2 Multiphase Nano-Nickel Hydroxide 108
2.5.3 Nickel-Metal Hydride Batteries 108
2.6 Sodium-Ion Batteries 112
2.6.1 Antimony-Based Intermetallic Alloy Anodes 112
2.7 Solar Cells 113
2.7.1 Star-Shaped Molecules 113
2.7.2 Dye-Sensitized Solar Cells 115
2.7.3 Perovskite 119
2.7.4 Control of Active Layer Nanomorphology 120
2.7.5 Phosphonium Halides as Processing Additives and Interfacial Modifiers 121
2.7.6 Polymeric Solar Cells 121
2.8 Fuel Cells 123
2.8.1 Porosity Additive 125
2.8.2 Electrolyte Membranes 126
2.8.3 Molybdenum Oxide 130
2.8.4 Nano-Metal Oxides 131
2.8.5 Coolant Additive 131
2.8.6 Membrane Exchange Humidifier 133
2.8.7 Poly(vinyl alcohol)/Titanium Dioxide Nanocomposites 134
3 Medical Uses 145
3.1 High Performance Additive Manufactured Scaffolds 145
3.1.1 Nanotechnology 145
3.1.2 Poly(caprolactone)Tricalcium Phosphate Scaffolds 146
3.1.3 Silk Fibroin Nanofibers 147
3.1.4 Calcium Phosphate, Hydroxyapatite, and Poly(d,l-lactic acid) 152
3.1.5 Propylene Fumarate Lactic Acid Copolymer 152
3.1.6 Thermosensitive Composite Gel 153
3.1.7 Biomimetic Wet-Stable Fibers 153
3.1.8 Poly(ester urea) from l-Leucine 154
3.1.9 Static Cell Seeding Versus Vacuum Cell Seeding 154
3.1.10 Controlled Drug Release 155
References 156
4 Lubricants 159
4.1 Fuels 159
4.1.1 Graphene Oxide 159
4.1.2 Deposit Control 160
4.2 Lubricant Additives 161
4.2.1 GL Ratings 161
4.2.2 Organophosphates 162
4.2.3 Crankcase Oils 162
4.2.4 Low Sulfur and Low Metal Additive Formulations 163
4.2.5 Lithium Soaps 166
4.2.6 Titanium Complex Grease Composition 171
4.2.7 Improving theWetting Properties of Ionic Liquids 176
4.3 Anti-Wear Additives 179
4.3.1 Ionic Liquids 179
4.3.2 Castor Oil Tris(diphenyl phosphate) 179
4.3.3 Bifunctional Hairy Silica Nanoparticles 180
4.3.4 Boron Thiophosphite 180
4.3.5 Hydroxyaromatic Compounds 181
4.4 Fluid Loss Control Additives 183
4.4.1 Graphene Oxide 183
4.4.2 Montmorillonite 183
4.5 Warm Mix Asphalt Additives 184
5 Concrete Additives 189
5.1 Properties of Concrete 189
5.1.1 Pozzolans 191
5.1.2 Calcium Aluminate Cement 191
5.1.3 Rutting of Bituminous Concrete 193
5.2 Set Retarders 193
5.2.1 Superplasticizers 194
5.3 Accelerators 194
5.3.1 Aqueous Dispersions of Silica 195
5.3.2 Non-Chloride Cement Accelerators 195
5.4 Dispersants and Thinners 196
5.4.1 Xylonic Acid 196
5.4.2 Thixotropy 197
5.4.3 Flowability 198
5.5 Defoamers 199
5.5.1 Ethoxylated Fatty Alcohol Acrylates 200
5.5.2 Hydroxyl Alkyl Acrylate 200
5.5.3 Tributyl Phosphate 202
5.5.4 Silicone Oils 202
5.5.5 Other Additives 202
5.6 Shrinkage Compensation 202
5.7 Permeability 203
5.7.1 Expanded Perlite 204
5.7.2 Pozzolanic Materials 204
5.7.3 Cracking Catalyst 205
5.8 Air Entraining Agents 206
5.8.1 Fluorochemical Surfactants 207
5.8.2 Superabsorbent Polymers 207
5.8.3 Rubber Crumb 208
5.8.4 Autoclaved Aerated Concrete 209
5.9 Corrosion Protection 210
5.9.1 Modified Hydrotalcites 210
5.9.2 Chloride Ion Scavenging 210
5.9.3 Dopamelanin 211
5.10 Superabsorbent Polymers 212
5.11 Fibers 212
5.11.1 Poly(oxymethylene) Fibers 212
5.12 Additives fromWastes 214
5.12.1 Waste Rubber 214
5.12.2 anomodified Concrete Additive 216
References 220
6 Other Uses 225
6.1 High Performance Additive for Powder Coatings 225
6.1.1 Antimicrobial Powder Coatings 225
6.2 Radiation Shielding 226
6.3 Superabsorbent Polymers 229
6.4 Laser Additive Manufacturing of High
Performance Materials 232
6.4.1 Laser Metal Deposition Additive Manufacturing 232
6.4.2 Hybrid Processes 233
6.5 High Temperature Cooling Application 234
References 236
Index 239
Tradenames 239
Acronyms 242
Chemicals 244
General Index 255
Chapter 1
Analysis and Separation Techniques
1.1 High Performance Liquid Chromatography
1.1.1 Ionic Liquids as Mobile Phase Additives
The popularity of ionic liquids has grown in several analytical separation techniques. Thus, the reports concerning the applications of ionic liquids are still increasing. The use of ionic liquids, mainly imidazolium-based, associated with chloride and tetrafluoroborate as mobile phase additives in high performance liquid chromatography (HPLC) has been reviewed (1).
Mostly, ionic liquids just function as salts, but keep several kinds of intermolecular interactions, which are useful for chromatographic separations. Both cation and anion can be adsorbed on the stationary phase, creating a bilayer. This gives rise to hydrophobic, electrostatic and other specific interactions with the stationary phase and solutes, which modify the retention behavior and peak shape (1).
1.1.1.1 Imidazolium Compounds
The beneficial effects of several ionic liquids as mobile phase additives in HPLC using an electrochemical detection for the determination of heterocyclic aromatic amines have been evaluated (2). The tested ionic liquids were 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, and 1-methyl-3-octylimidazolium tetrafluoroborate. These compounds are shown in Figure 1.1.
Figure 1.1 Ionic liquids.
Several chromatographic parameters have been evaluated in the presence or absence of ionic liquids, or using ammonium acetate as the most common mobile phase additive, with three different C18 stationary phases. The effect of the acetonitrile content was also studied. Acetonitrile is shown in Figure 1.2.
Figure 1.2 Acetonitrile.
Best resolution, lower peak-widths, and lower retention factors were obtained when using ionic liquids rather than ammonium acetate as mobile phase additives. The best chromatographic conditions were found when using 1-butyl-3-methylimidazolium tetrafluoroborate as the mobile phase additive (2).
1-Butyl-3-methylimidazolium chloride, cf. Figure 1.3, 1-octyl-3-methylimidazolium chloride, and 1-decyl-3-methylimidazolium chloride were used as mobile phase additives in the HPLC to simultaneously separate phenoxy acid herbicides and phenols at neutral pH (3). It was found that when using 1-butyl-3-methylimidazolium chloride, a good baseline separation and good chromatograms for all the acid compounds were obtained on a normal reversed phase C18 column.
Figure 1.3 1-Butyl-3-methylimidazolium chloride.
The retention time of the target acid compounds was shortened with the increase of the alkyl chain length and the concentrations of ionic liquids, probably due to the delocalization of the positive charge on the imidazolium cation, the repulsion between chlorine ions of ionic liquids and the acid compounds, as well as the stereohindrance effect (3).
Extraction of Sudan Dyes. Sudan dyes are typically used as coloring additives in the manufacturing of wax, textile, and floor and shoe polishes (4, 5). Sudan I has been classified as a category 3 carcinogen by the International Agency for Research on Cancer (IARC). Also, Para Red could be a genotoxic carcinogen (6). The structures of the coloring additives are shown in Figure 1.4. The chemical names of the dyes are summarized in Table 1.1.
Figure 1.4 Sudans and Para Red.
Table 1.1 Chemical names of the dyes.
Short name Chemical name Sudan I 1-[(2,4-Dimethylphenyl)azo]-2-naphthalenol Sudan II 1-(Phenylazo)-2-naphthol Sudan III 1-(4-Phenylazophenylazo)-2-naphthol Sudan IV o-Tolyazo-o-tolylazo-ß-naphthol Para Red 1-p-Nitrobenzeneazo-2-naphtholA method for the analysis of such dyes has been developed. The method is based on coupling of ionic liquid-based extraction with HPLC. In this way, Sudan dyes and Para Red in chili powder, chili oil, and food additive samples can be found.
Two ionic liquids, i.e., 1-butyl-3-methylimidazolium hexafluorophosphate, cf. Figure 1.5, and 1-octyl-3-methylimidazolium hexafluorophosphate have been compared as extraction solvents. It was found that 1-octyl-3-methylimidazolium hexafluorophosphate showed higher recoveries for each analyte.
Figure 1.5 1-Butyl-3-methylimidazolium hexafluorophosphate.
Also, the conditions for the extraction of Sudan dyes and Para Red were optimized. Under optimal conditions, a good reproducibility of extraction performance was obtained, with relative standard deviation values of 2.0-3.5% (7).
The ionic liquids were prepared according to a previously reported method (8, 9). The Sudan dyes and Para Red standard solutions were obtained from Zhejiang Entry-Exit Inspection and Quarantine Bureau (Hangzhou, China).
The detection limits and the recoveries are summarized in Table 1.2.
Table 1.2 Detection limits and recoveries for Sudan dyes and Para Red (7).
Material Detection limit[µg kg-1] Recovery
[%] Chili powder 7.0-8.2 76.8-109.5 Chili oil 11.2-13.2 70.7-107.8 Food additives 11.2-13.2 70.7-107.8
Nucleotides Separation. A method for the separation of nucleotides has been developed (10). These nucleotides include 5´-monophosphate adenosine, 5´-monophosphate cytidine, 5´-monophosphate uridine, 5´-monophosphate guanosine, and 5´-monophosphate inosine. Some of these compounds are shown in Figure 1.6.
Figure 1.6 Nucleotides.
The essential feature of the method is that 1-alkyl-3-methylimidazolium salts are used as mobile phase additives, resulting in a baseline separation of nucleotides without the need for gradient elution and organic solvent addition, as usually used in reversed phase HPLC (10).
Amine Separation. By varying the lengths and branching of alkyl chains of the anionic core and the cationic precursor, it is possible to design solvents for specific applications. Because of these characteristic properties, ionic liquids are widely used as new solvent media in heterogeneous catalysis, synthesis, electrochemistry, sensors, battery applications, analysis and separation techniques (11).
Some amines, including benzidine, benzylamine, N-ethylaniline and N,N´-dimethylaniline could be separated using ionic liquids as additives for the mobile phase in HPLC (12).
The compounds 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIm][BF4]), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIm][BF4]) and 1-butyl-3-methylimidazolium bromide ([BMIm]-[Br]) were used as ionic liquids. Some of these compounds are shown in Figure 1.7. Some properties are summarized in Table 1.3.
Figure 1.7 Ionic liquids.
Table 1.3 Properties of certain ionic liquids (8, 12, 13).
Compound Melting point [°C] Density [g ml-1] 1-Ethyl-3-methylimidazolium tetrafluoroborate 6 1.29 1-Butyl-3-methylimidazolium tetrafluoroborate -81 1.17 1-Hexyl-3-methylimidazolium tetrafluoroborate -66 1.29 1-Butyl-3-methylimidazolium bromide -72 1.44The effects of the length of alkyl chain or counterions on different ionic liquids and their concentrations on the separation of these analytes have been assessed (12).
The differences between the ionic liquids and tetrabutyl ammonium bromide on the separation of o-phthalic acid, m-phthalic acid, and p-phthalic acid have been compared. The results indicated that ionic liquids act as ion-pair reagents, although their hydrophobicity and hydrogen bonding also play important roles (12).
Catecholamines. The use of 1-alkyl-3-methylimidazolium salts and N-butyl-pyridinium salts as mobile phase additives for the separation of catecholamines in reversed phase HPLC has been reported (14). As catecholamines, norepinephrine, epinephrine and dopamine were investigated. These compounds are shown in Figure 1.8.
Figure 1.8 Catecholamines.
A good separation could be achieved with these additives. The effects of pH of the mobile phase, the...
