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Sergiy Antonyuk Editor
Particles in
Contact
Micro Mechanics, Micro Process
Dynamics and Particle Collective
Particles in Contact
Sergiy Antonyuk
Editor
Particles in Contact
Micro Mechanics, Micro Process Dynamics
and Particle Collective
123
Editor
Sergiy Antonyuk
Institute of Particle Process Engineering
Technische Universität Kaiserslautern
Kaiserslautern, Germany
ISBN 978-3-030-15898-9 ISBN 978-3-030-15899-6 (eBook)

https://doi.org/10.1007/978-3-030-15899-6
© Springer Nature Switzerland AG 2019
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt from
the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, expressed or implied, with respect to the material contained
herein or for any errors or omissions that may have been made. The publisher remains neutral with regard
to jurisdictional claims in published maps and institutional affiliations.
This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
This book is dedicated in memory of
Professor Jürgen Tomas—an outstanding
scientist, colleague and friend.
Preface
The properties and behaviour of particulate products, such as powder materials,

agglomerated or coated materials, fillers, active ingredients or pigments and natural
substances, like soils, sludge or aerosols, are significantly determined by interac-
tions between fine solid particles in granular matter. The production, handling and
transport processes of the solid products are also heavily influenced by the inter-
particle interactions. For the optimization of existing solid processes and devel-
opment of novel particulate products, the understanding and description of
physicochemical microprocesses, which take place during approaching, direct
contact and detachment of adhesive fine particles (from a few nanometers to
100 micrometers) are needed. Therefore, the description of macroscopic phenom-
ena and properties of particulate matter consisting of many particles needs a basic
understanding of the micromechanical and adhesive interactions of single particles
in contact. They can be characterized by stress–strain, force–displacement, torgue–
angle and potential–distance relationships for six degrees of freedom for the
translation and rotation of particles in contact. New scientific developments in the
field of simulations as well as measuring technique make it possible to understand
and describe these relationships in the form of contact or potential models. These
interaction models based on the physical parameters of individual particles can be
used in modern particle-based simulation methods, such as Discrete Element
Method or Molecular Dynamics, to provide an accurate prediction of the mor-
phology, microstructure, deformation and flow behaviour and distribution of the
properties of particulate systems in industrial processes.
The German Research Foundation (Deutsche Forschungsgemeinschaft, DFG)
has supported an international research program in the form of Priority Program
(SPP 1486) “Particles in Contact—Micro Mechanics, Micro Process Dynamics and
Particle Collective” from 2010 to 2017. This book summarizes the research results
of this joint research project obtained by 27 cooperating institutes from Germany,
Austria, The Netherlands and Switzerland. The coordinator of this program was
Prof. Jürgen Tomas from the Otto von Guericke University Magdeburg (Germany).
This program was created and successfully carried out thanks to his innovative
ideas, his enthusiasm for powder technology that has brought the scientists from
vii
viii Preface
different research areas together into this research project. Unfortunately, he passed
away too early. Since 2015, Prof. Sergiy Antonyuk from the Technische Universität
Kaiserslautern has taken over the coordination of this program.
We want to thank DFG for the financial support, and specially Dr.-Ing. Bernd
Giernoth, Dr.-Ing. Georg Bechtold, Dr. Simon Jörres and Ms. Anja Kleefuß for
their excellent coordination and support for the research activities of the SPP.
I am grateful to my Ph.D. students Vanessa Puderbach, Robert Hesse, Philipp
Lösch, Dominik Weis, and Oleg Urazmetov, who caught misprints in the proofs of
this book.
Kaiserslautern, Germany Sergiy Antonyuk

December 2018
Contents
Analysis of Adsorbates and Interfacial Forces at Metal Oxide

Interfaces at Defined Environmental Conditions . . . . . . . . . . . . . . . . . . 1
A. G. Orive, C. Kunze, B. Torun, T. de los Arcos and G. Grundmeier
Understanding and Manipulation of Nanoparticle Contact Forces
by Capillary Bridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Hans-Joachim Schmid, Guido Grundmeier, Michael Dörmann,
Alejandro González Orive, Teresa de los Arcos and Boray Torun
Microwave Emission During the Impact Compaction
of Particle Bed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Sergej Aman, Alexander Aman and Werner Hintz
Formation, Deformation, Rolling and Sliding of Particles and Particle
Aggregates: Mechanisms and Applications . . . . . . . . . . . . . . . . . . . . . . . 89
Laurent Gilson, Jennifer Wenzl, Maxime Paven, Michael Kappl,
Hans-Jürgen Butt, Doris Vollmer and Günter K. Auernhammer
Contact Models and DEM Simulation of Micrometer-Sized Particles
and Agglomerates at Static Loading Based on Experimental
Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Philipp Grohn, Dominik Weis, Ulrich Bröckel, Stefan Heinrich
and Sergiy Antonyuk
DEM Analysis of Breakage Behavior of Bicomponent
Agglomerates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Maksym Dosta, Matthias Weber, Volker Schmidt and Sergiy Antonyuk
Contact Mechanisms in Ultrasound-Agitated Particulate Systems . . . . . 185
Claas Knoop, Tobias Wollborn and Udo Fritsching
Capillary Interaction in Wet Granular Assemblies: Part 1 . . . . . . . . . . 239
Stephan Herminghaus, Ciro Semprebon and Martin Brinkmann
ix
x Contents
Capillary Interaction in Wet Granular Assemblies: Part 2 . . . . . . . . . . 277

Falk K. Wittel, Roman Mani, Konstantin Melnikov, Filippo Bianchi
and Hans J. Herrmann
Sintering—Pressure- and Temperature-Dependent Contact Models . . . . 311
T. Weinhart, R. Fuchs, T. Staedler, M. Kappl and S. Luding
A Contact Model for the Discrete Element Simulations of Aggregated
Nanoparticle Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
Valentin Baric, Jens Laube, Samir Salameh, Lucio Colombi Ciacchi
and Lutz Mädler
Determination of the Adhesion Forces of Magnetic Composite
Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Johannes Knoll, Frank Rhein and Hermann Nirschl
Deformation and Friction at the Microscale—From Model
Experiments to Process Characterization . . . . . . . . . . . . . . . . . . . . . . . . 385
Wolfgang Peukert and Stefan Romeis
Measurement of the Adhesion Moment of a Particle on a Wall
in a Gaseous Environment and Comparison to Simulated Data . . . . . . . 417
Alexander Haarmann and Eberhard Schmidt
Nanoindentation Based Colloid Probe Technique: A Unique
Opportunity to Study the Mechanical Contact of Individual
Micron Sized Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
Thorsten Staedler, Katharina Diehl, Regina Fuchs, Jan Meyer,
Aditya Kumar and Xin Jiang
The Importance of Interactions Between Carrier and Drug Particles
for the Application in Dry Powder Inhalers . . . . . . . . . . . . . . . . . . . . . . 457
Sarah Zellnitz, Niklas Renner, Yan Cui, Regina Scherließ,
Martin Sommerfeld, Hartwig Steckel and Nora Urbanetz
Rapid Impact of Nanoparticles on Surfaces . . . . . . . . . . . . . . . . . . . . . . 517
Alfred Weber, Christian Schöner, Manuel Gensch, Alexander Werner
and Thorsten Pöschel
Stochastic Nature of Particle Collisions and its Impact on Granular
Material Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565
Nina Gunkelmann, Dan Serero, Aldo Glielmo, Marina Montaine,
Michael Heckel and Thorsten Pöschel
Non-ohmic Properties of Particle Layers in Electrostatic
Precipitators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
Damian Pieloth, Helmut Wiggers and Peter Walzel
Contents xi
Structure of Sheared Cohesive Granular Bulk . . . . . . . . . . . . . . . . . . . . 607

Lothar Brendel, Alexander Weuster, Dietrich E. Wolf, Harald Zetzener,
Stephan Strege, Lutz Torbahn, Arno Kwade, Lisa Handl
and Volker Schmidt
Improved Flowability of Ultrafine, Cohesive Glass Particles
by Surface Modification Using Hydrophobic Silanes . . . . . . . . . . . . . . . 631
Zinaida Todorova, Steffi Wünsche and Werner Hintz
Analysis of Adsorbates and Interfacial
Forces at Metal Oxide Interfaces
at Defined Environmental Conditions
A. G. Orive, C. Kunze, B. Torun, T. de los Arcos and G. Grundmeier
Introduction
Adhesion forces between ensembles of micro- and nanoparticles are central in pro-
cesses such as fluidization, agglomeration and sintering [1]. These effects find appli-
cations in an extensive range of technical fields that include the development of
pharmaceutical powders, paints, and solar cells [2, 3].
Contact forces between oxide nanoparticles are strongly dependent on the surface
chemistry, the presence of adsorbate layers and the environmental conditions [4].
High-energy oxide surfaces under ambient conditions spontaneously adsorb organic
molecules and water. This adsorption leads to reduced surface energies. While the
existence of atmospheric contaminations on oxide surfaces is routinely observed in
surface analytical studies, their surface concentration and composition is often not
perfectly controlled.
For most technological applications, assemblies of micro and nanoparticles will
be necessarily utilized under normal ambient experimental conditions. As a conse-
quence, the prevalence of water layers adsorbed onto the particle surfaces which are
in contact with humid air needs to be taken into account. Indeed, capillary forces
due to capillary condensation are particularly interesting since, when present, they
usually dominate the inter-particle adhesion interactions. Over the last few years,
both theoretical and experimental approaches have been carried out to propose a
unified model which might account for the relevance of contact forces between par-
ticles under humid conditions [5, 6]. In particular the high-energy surfaces of micro-
and nano-metal oxide particles experience the spontaneous adsorption of molecule
A. G. Orive · C. Kunze · B. Torun · T. de los Arcos · G. Grundmeier (B)

Institute of Technical and Macromolecular Chemistry, University Paderborn, Paderborn,
Germany
e-mail: g.grundmeier@tc.upb.de; guido.grundmeier@uni-paderborn.de
© Springer Nature Switzerland AG 2019 1

S. Antonyuk (ed.), Particles in Contact,
https://doi.org/10.1007/978-3-030-15899-6_1
2 A. G. Orive et al.
adsorbates and water, which gives rise to a reduced surface energy. At this point,
it is worth noting that although the afore-mentioned molecular adsorptions due to
atmospheric exposure are well-known and easily identified by analytical techniques
in interfacial surface studies, their quantitative surface concentration and composi-
tion is often not stated or it is poorly characterized. In particular, nano-contact force
studies carried out at gas/solid interfaces, e.g. by means of atomic force microscopy
(AFM), are often performed upon rather ill-defined conditions.
The quantification of the contact forces occurring between micro- and nanoparti-
cles can be straightforwardly assessed by force spectroscopy measurements by means
of AFM [7]. In a seminal contribution, Harrison et al. [8] collected experimental and
theoretical results coming from 28 different approaches dealing with the assessment
of capillary forces in the nanoparticle regime. It was clearly stated that the impact
of capillary forces on particle interfacial adhesion depends on a nontrivial combi-
nation of the particle shape, size, deformability, adsorbate layers, surface roughness
and hydrophilicity [6, 9]. Indeed, Farshchi-Tabrizi et al. [7] showed that the con-
tact geometry has a critical influence on the humidity dependence of the adhesion
force. They addressed the contact forces occurring between regular AFM tips and
also the result of attaching particles to them and different solid samples, smooth and
rough surfaces. Interestingly, the dependence between adhesion forces and humidity
register for hydrophilic surfaces exhibited two distinct behaviors: a maximum or
an increasing linear growing behavior. A new numerical models considering both
surface roughness and cantilever shape that accurately estimates the quantification
of the meniscus force was successfully proposed.
Regarding the presence of molecule adsorbate layers, Gojzewski et al. [10] ele-
gantly introduced the measurement of the contact forces arising between the surfaces
of silicon nitride AFM cantilevers and self-assembled monolayers (SAM) on gold as
a function of relative humidity by means of dynamic force spectroscopy. Methylene-
and hydroxyl-terminated SAMs were used as model hydrophobic and hydrophilic
surfaces, respectively. The adhesion forces registered for the hydrophilic SAMs were
noticeably higher than those obtained for the hydrophobic ones, even at low humidity
values. The latter cannot be thus not only attributed to the formation of hydrogen
bridges between hydroxyl groups from the SAM and silanol functionalities of the
AFM tip, but also to the strength of the capillary forces.
Taking all the afore-mentioned facts into account, it is clear that AFM measure-
ments carried out under ultra-high vacuum or clean (pure) electrolytes offer the
advantage of working with a precisely defined interface chemistry. The aim of the
work presented here was to analyze (characterize) the impact of poorly defined ambi-
ent surface contamination such as water and organic molecule adsorbates by directly
removing them or replacing them by model adsorbates. In the following, TiO2 , ZnO
and Al2 O3 surfaces have been considered as model metal oxides with high surface
energy as promising candidates/platforms for fundamental adhesion force studies. In
particular, AFM-based methods such as nanoshaving (AFM scratching), UHV-based
nanocontact force studies and single molecule force spectroscopy were applied. In
addition, in situ FTIR surface spectroscopy was performed to analyze the behavior
of some molecule adsorbates under humid conditions.
Analysis of Adsorbates and Interfacial Forces at Metal … 3
Materials and Methods
Materials and Surface Preparation
Materials and Chemicals
Rutile TiO2 single crystals with crystallographic (100) and (110) orientations in the
size of 10 mm × 10 mm × 0.5 mm were obtained from Mateck GmbH (Juelich,
Germany) and CrysTec (Germany), respectively. Al2 O3 (11–20) single crystalline
substrates of 20 mm × 20 mm × 0.5 mm were also purchased from Mateck GmbH
(Juelich, Germany).
All chemicals were of p.a. grade (analytical reagent grade) and used without
any further purification. Nonadecanoic acid (97%) was purchased from Fluka.
Octadecylphosphonic acid (97%) and hexylphosphonic acid were obtained from
Alfa Aesar. α-Mercapto-ω-amino PEG hydrochloride (HS–PEG–NH2 × HCl, PEG-
MW: 10,000 Da), A-Hydroxy-ω-mercapto PEG (HO–PEG–NHCO–CH2 –CH2 –SH,
PEG-MW: 10,000 Da), A-Methoxy-ω-mercapto PEG (CH3 O–PEG–SH, PEG-MW:
10,000 Da) were acquired form Rapp Polymere GmbH. Absolute ethanol, used as
a solvent and for general cleaning purposes, was purchased from VWR Interna-
tional. Hydrofluoric acid (40%) was obtained from Merck KGa. Ultrapure water
was obtained from an Ultraclear TWF (SG Wasseraufbereitung, Barsbüttel, Ger-
many) system with a maximum electrical conductance of 0.055 μS cm−1 . RCA-1
solution, i.e. 5:1:1; purified water, ammonia solution 30%, hydrogen peroxide 30%,
was used for both etching and cleaning purposes.
Preparation of Rutile TiO2 (110) and (110) Single Crystalline Surfaces

[11, 12]
In order to prepare surfaces stable under ambient conditions, TiO2 (100) single crys-
talline surfaces were prepared from commercial TiO2 rutile single crystals. The pro-
cedure followed consisted of a pre-cleaning step, where the TiO2 crystals were soni-
cated in ultrapure water, followed by wet chemical etching, and finally an annealing
step according to the methodology developed by Nakamura et al. [13] and Yamamoto
et al. [14]. In order to avoid possible contamination of the crystals during the prepa-
ration, the etching was performed in a PTFE vessel. (100) and (110) oriented TiO2
crystals were etched in 20% HF solution for 20 min. After the etching process, the
crystals were intensively rinsed with ultrapure water and dried in a stream of pure
nitrogen gas. The crystals were then deposited into a tube furnace with Al2 O3 walls
and annealed at 680 °C for 48–72 h in ambient air. A slow heating and cooling rate of
3 °C/min (ramping time of 3.5 h) was selected in order to minimize both mechanical
stress in the crystal and in the furnace tube. The quality of the so-prepared TiO2 (100)
and (110) single crystals was finally assessed by means of AFM and LEED. A non-
conventional 1 × 3 superstructure was obtained in the LEED pattern registered for

the as-prepared TiO2 (100) surfaces.
Preparation of Al2 O3 (0001) and (11–20) Single Crystals [11]
In order to produce well-defined Al2 O3 (0001) and Al2 O3 (11–20) single crystalline
surfaces, alkaline and acidic etching procedures were applied to the as-received com-
mercial substrates according to a well-established methodology published elsewhere
[11]. Briefly, the as-received substrates were immersed into RCA-1 (5:1:1; purified
water, ammonia solution 30%, hydrogen peroxide 30%) solution for 2 min at 70 °C
to remove organic contaminants. Then, they were subsequently immersed into a
phosphoric acid (85%) aqueous solution for 2 min, rinsed with ultra-pure water, and
dried with nitrogen. The as-treated crystals were then annealed under an ambient
atmosphere at 1450 °C for 36 h.
Additionally, in the case of Al2 O3 (11–20) the single crystals were again immersed
into phosphoric acid (85%, 2 min), rinsed with ultra-pure water, and dried with
nitrogen. The goal was to simulate the acidic treatment conventionally used in the
conditioning Al-alloy surfaces before being exposed to adhesive compounds. A rep-
resentative AFM image of such prepared surfaces is shown in Fig. 1.
Fig. 1 AFM topography

image of Al2 O3 (11–20)
single crystal cleaned with
RCA-1, etched with
concentrated phosphoric
acid, heat treated at 1450 °C,
and finally etched in
concentrated phosphoric
acid. Reprinted from [15]
with permission from
Elsevier
Adsorption of Organic Monolayers on TiO2 and Al2 O3 Single Crystalline

Surfaces [11]
In order to carry out fundamental studies about the interaction between carboxylic
acids with well-defined TiO2 surfaces, nonadecanoic acid (NDCA) was selected
as a model system to characterize the adsorbate formation process onto TiO2 (100)
single crystalline substrates [11]. In this regard, freshly prepared TiO2 single crystals
were immersed into a 1 mM NDCA ethanolic solution for 12–16 h. After that, the
as-modified substrates were rinsed in ethanol and dried in a nitrogen stream.
Additionally, with the aim to remove the scarcely defined carbon contaminations
due to atmospheric contamination, TiO2 (110) substrates were chemically modified
by self-assembly (SA) with octadecylphosphonic acid (ODPA) molecule layer. In this
regard, freshly prepared and annealed TiO2 (110) single crystals were immersed into a
1 mM ODPA ethanolic solution for 16 h. The as-modified substrates were thoroughly
rinsed in ethanol and dried in a nitrogen stream. This approach was carried out to
create a defect-free surface covered by a well-defined aliphatic adsorbate layer as
a reference surface to assess the impact of such aliphatic-based film on interfacial
contact forces [12].
ODPA and hexyl phosphonic acid (HPA)-based organic films onto Al2 O3 (0001)
single crystal were prepared by self-assembly. The freshly chemically etched and
thermally annealed aluminum oxide substrates were immersed into 1 mM molecule
(ODPA or HPA)-containing ethanolic solution for 12 h. The as-modified crystals were
thoroughly rinsed with ultrapure ethanol, dried in nitrogen stream, and immediately
used.
AFM Instrumentation
UHV-AFM
UHV AFM imaging and Force-distance curve (F-D) spectroscopy were carried out
by using a VT-AFM XA (Oxford Instruments, Taunusstein, Germany) microscope
(Fig. 2). AFM images were collected in contact mode. CSC17 cantilevers (resonant
frequency of 13 kHz, spring constant of 0.18 N/m, and tip radius of 8 nm) purchased
from Mikromasch (Bulgaria) were used. For AFM-based F-D spectroscopy mea-
surements, data obtained from 16 × 16-point grids over 2.0 × 2.0 μm2 areas were
collected at room temperature for statistical purposes. The AFM tip was approached
and retracted over the sample surface at 1 μm/s for a 500 nm tip-sample separation.
The cantilevers were calibrated according to their deflection sensitivity, obtained
from the slope of the repulsive regime, and the spring constant, which was obtained
by means of the thermal noise method [16].
Fig. 2 Illustration of the UHV analytical setup allowing the measurement of surface chemistry and
contact forces. (1) preparation chamber; (2) analysis chamber; (3) AFM chamber; (4) gas and water
dosing system
Ambient Pressure AFM
AFM imaging was carried out by using a JPK Nanowizard II Ultra (JPK Instruments
AG, Berlin, Germany) operating in air and at room temperature with a scan rate
of 1 Hz. The topographical features exhibited by pristine TiO2 (100) single crystal
surfaces were characterized in contact mode in a window loading force range of
2–5 nN. In this case, DP17 silicon cantilevers (12 kHz, 0.17 N/m), purchased form
Mikromasch, were used. However, for the AFM characterization of NDCA-modified
TiO2 (100) substrates, alternating contact mode (AC) was chosen. For the latter, an
amplitude corresponding to a 90% of the free-air amplitude was maintained constant
during the profiling. Both AC AFM imaging and nanoshaving experiences were car-
ried out using NSC15 AFM tips (320 kHz, 40 N/m), acquired from Mikromasch. In
the nanoshaving and nanografting processes, an organic molecule monolayer (typ-
ically prepared by self-assembly) is removed/altered as a consequence of AFM tip
ploughing. Essentially, when high enough loading forces are applied in a pure solvent
with the AFM tip, the latter is expected to scratch the modified surface and subse-
quently remove the organic film, unveiling thus the underlying substrate surface.
This procedure is known as nanoshaving. If this process is carried out when other
secondary molecules are also present in the solvent, then a fast chemisorption of the
latter onto the shaved area can be obtained, i.e. nanografting [17]. It is worth noting
that although the organic layer is removed as a consequence of AFM tip plough-
ing, no noticeable damage on the single crystalline surfaces can be detected for the
loading force window range considered.
Single molecule force spectroscopy experiences on Al2 O3 (11–20) single crystals
were carried out using an MFP-3D-SA (Asylum Research) microscope equipped
with an anti-vibration system. A fluid cell (Fluid Cell Lite from Asylum Research)
was employed to obtain the corresponding force-distance curves in 10 mM NaClO4
aqueous solution at pH 6. In order to achieve good reproducibility, several hundred
force curves were recorded in each experiment. The rupture events were evaluated
with Igor-Pro software. Note that only a fraction (10–30%) of all curves showed
rupture events. In those cases, the force recorded at the rupture point was noted
and used to build an additional set of statistical data. A Gaussian fit was applied to
determine the mean force value.
Modification of AFM-Tips
TiO2 Coated AFM-Tips
NSC19 AFM cantilevers (65 kHz, 0.5 N/m), acquired from Mikromasch, were
modified with 150 nm thick titanium coating by means of plasma-enhanced PVD.
A titanium target was sputtered by a DC plasma in pure Argon atmosphere at
0.2 × 10−3 mPa at a mean power of 2 kW and 300 V bias voltage. Under these
experimental conditions, a deposition rate of 14 nm/min was obtained. In order to
completely oxidize the titanium coating of the cantilevers, the latter modified AFM
tips were annealed in air at 600 °C for 16 h.
Macromolecular Modification of AFM Tips
Gold-coated silicon cantilevers HQ:CSC17 (13 kHz, 0.18 N/m), acquired from
Mikromasch, were cleaned according to a well-stablished procedure published else-
where [15]. Briefly, as-received cantilevers were immersed into an RCA-1 solution
for 2 min. at 70 °C in order to remove organic contaminants. After that, the tips were
rinsed with ultrapure water and subsequently dried in a nitrogen stream.
OH-Functionalization
The solvent cleaned gold-coated cantilevers were introduced into a 1 mM A-Hydroxy-

ω-mercapto PEG-containing ultrapure water solution for t = 4 h.
NH2 × HCl-Functionalization
The solvent cleaned gold-coated cantilevers were introduced into a 1 mM

α-Mercapto-ω-amino PEG hydrochloride-containing ultrapure water solution
for t = 4 h.
OCH3 -Functionalization
The solvent cleaned gold-coated cantilevers were introduced into a 1 mM α-Methoxy-

ω-mercapto PEG-containing ultrapure water solution for t = 4 h.
XPS Analysis
XPS measurements were performed in an Omicron ESCA+ System (Omicron

NanoTechnology GmbH, Germany). The element spectra were recorded at pass
energies of 25 eV. A monochromated Al Kα (1486.3 eV) X-ray source with a spot
diameter of 600 μm was used. The calibration of the spectra was done by using the
position of the C 1s core level peak of adventitious carbon (binding energy, BE =
285 eV) as a reference. For data evaluation, the CasaXPS software was used [18].
For the quantitative analysis of the surface chemistry of the prepared crystals,
angle-resolved XPS experiments were performed. XPS spectra were recorded at take-
off angles of the photoelectrons from 70° to 10° with respect to the surface plane. The
probing depth d can be calculated as a function of the take-off angle [19] according
to d = λsin, where λ is the inelastic mean free path of the photoelectrons.
LEED Instrumentation
Omicron Spectra LEED optics were employed at an incident angle close to 90° with
respect to the surface for LEED experiences. With the aim to obtain high-quality
LEED images, the beam energy was adjusted from 80 to 120 eV. The as-registered
LEED patterns of the corresponding surfaces were simulated and compared using
the software LEEDpat30.
Results
Analysis of Disordered Molecular Adsorbates by Means

of Nanoshaving and XPS Analysis
The molecular adsorbate formation of alkanehydroxamic and carboxylic acids on

various metal oxides was investigated by Folkers et al. [20]. They observed the
formation of self-assembled hydroxamic monolayers, which they attributed to the
high complexation constant of the hydroxamic acids with metal ions as opposite
to carboxylic acids. Thus, in the case of carboxylic acids adsorbed onto amorphous
TiO2 oxide films on Ti no self-assembly process was observed. The authors proposed
that this behaviour was mainly governed by the acid to neutral behavior of the TiO2
oxide film. Therefore, in this section we address the adsorption of model molecules
with the aim of getting a good understanding of particle–wall interactions in the
presence of a well-defined adsorbate under ambient conditions. Nonadecanoic acid
(NDCA) was chosen as a model molecule to simulate typical adsorbates present in
ambient atmosphere. The reasoning behind was that (i) the carboxylic acid group can
mimic the chemical functionalities of molecules present at atmospheric conditions,
(ii) the well-defined composition of the aliphatic chain results in an intense carbon
signal in XPS experiments and (iii) it leads to a measurable height contrast in AFM
based nanoshaving investigations. NDCA monolayers were prepared on a TiO2 (100)
single crystal by self-assembly from NDCA-containing ethanolic solutions [21].
Nanoshaving
The topographical features exhibited by adsorption of NDCA molecules onto

TiO2 (100) single crystal surfaces were investigated by AFM operating in air in
AC mode [22]. By comparison to the smooth atomically flat terraces of pristine
TiO2 (100), rounded nanostructured islands or domains decorating the terraces can be
observed, which are attributable to a sub-monolayer coverage of NDCA molecules.
The ploughing of a 500 × 500 nm2 area with the AFM tip in contact mode with a
significant high value of loading force, leads to the removal of the adsorbed NDCA
molecules takes place (see Fig. 3).
As a consequence of the nanoshaving process, pristine areas of TiO2 (100) terraces
are uncovered. This is an indication that the NDCA adsorbate layer is easily removed
from the surface. By carrying out cross section profiles along both the outer NDCA
coated and the nanoshaved areas, a corrugation of 120 pm could be measured. The
latter value is noticeably lower than that expected for a tightly packed monolayer of
NDCA molecules arranged in a slightly tilted standing up configuration, since the
theoretical length of the NDCA molecules is in in the range of 2 nm. Consequently,
the formation of a disordered film together with a low fractional surface coverage
of NDCA molecules can be concluded from the analysis of the presented AFM
data. These results hint at a poor interaction between the anchoring carboxylate
Fig. 3 Left hand side: Nanoshaving on an NDCA covered TiO2 (100) surface shows the disordered
structure of the adsorbate layer, the scan size is 1 × 1 μm2 . Right hand side: cross section of the
area marked at the left. Reprinted from [22] with permission from Elsevier
groups and the TiO2 (100) surface. The result is that NDCA molecules exhibiting
carboxylate functional/anchoring groups, reversible adsorbed at active TiO2 (100)
adsorption sites, stay rather mobile due to relatively weak interactions.
XPS Analysis
The TiO2 substrate was characterized by XPS before and after NDCA adsorption.
The results of measurements of the pristine TiO2 (100) surface measured at different
take-off angles is shown in Table 1. Titanium, oxygen and carbon were found at the
surface. The atomic percentage of carbon increases when the photoelectron take-off
angle is decreased, which indicates that the carbon is associated to an adsorbate film
formed at the crystalline surface by exposure to air (adventitious carbon).
Most importantly, in comparison to the spectrum obtained for TiO2 (100) single
crystals prepared in UHV conditions where the O 1s signal is exclusively originated
from O−2 species, [23] the high resolution O 1s AR-XP core level peaks exhibit a
profile with different components that can be assigned to the presence of hydrox-
ides, adsorbed water and carboxylic groups. Indeed, the increase in the O/Ti ratio
when the take-off angle is reduced hints at an oxygen enrichment of the surface
supported by the surface RO−1 /O2− and RO−2 /O2− contributions [11], indicating a
Table 1 Surface composition Angle (°) O 1s (at.–%) Ti 2p 3/2 C 1s (at.–%)

of TiO2 (100) surface as at 530.2 eV (at.–%) at at 285 eV
measured by XPS at varying 458.8 eV
take-off angles with respect to
the surface plane (from [11]) 70 63.2 ± 0.5 27.9 ± 0.5 8.9 ± 0.5
40 62.5 ± 0.5 24.7 ± 0.5 12.8 ± 0.5
20 61.3 ± 0.5 19.0 ± 0.5 19.7 ± 0.5
10 51.2 ± 0.5 13.8 ± 0.5 35.0 ± 0.5
Table 2 Surface composition Angle (°) O 1s (at.–%) Ti 2p 3/2 C 1s (at.–%)

of the NDCA covered at 530.2 eV (at.–%) at at 285 eV
TiO2 (100) crystal as 458.8 eV
measured by XPS at varying
take-off angles with respect to 70 54.1 ± 0.5 22.6 ± 0.5 23.2 ± 0.5
the surface plane (from [11]) 40 52.6 ± 0.5 18.2 ± 0.5 29.2 ± 0.5
20 41.7 ± 0.5 13.9 ± 0.5 44.4 ± 0.5
10 29.1 ± 0.5 8.9 ± 0.5 62.0 ± 0.5
Fig. 4 C 1s spectrum of
NDCA covered TiO2 crystal
at varying take-off angles.
For ease of comparison, the
spectra were normalized and
shifted vertically. The
vertical dashed lines mark
the positions of the different
components of the C 1s peak.
Reprinted from [11] with
permission from Elsevier
hydroxide-terminated surface. Consequently, it could be concluded that a layer of

surface hydroxides is ubiquitously present on the TiO2 (100) single crystals prepared
under ambient conditions.
The adsorption of NDCA on TiO2 could also be proven by XPS by the significantly
increased carbon concentration in comparison to that exhibited by the bare TiO2 (100)
substrate (see Table 2).
An extensive XPS analysis of the NDCA-coated TiO2 crystals exhibited a C 1s
signal with a peak width of 1.25 eV of the C–C component at a takeoff angle of 10°
as depicted in Fig. 4.
Fig. 5 O 1s spectra of the

NDCA covered TiO2 (100)
surface measured at the same
take-off angles as in Fig. 4.
For ease of comparison, the
spectra were normalized and
shifted vertically. Reprinted
from [11] with permission
from Elsevier
The as-prepared NDCA adsorbate film exhibits the characteristic C 1s spectrum

expected for a long chain carboxylic acid, as can be seen in Fig. 4. The registered
ratio of C–C/COO is close to 16–18 range, which corresponds to the expected stoi-
chiometry of NDCA. Thus, the undefined original layer of adventitious carbon has
been replaced in this case by a well-defined layer of NDCA molecules, most likely
due to the stabilizing effect of intermolecular long aliphatic chain van der Waals
interactions.
Additionally, the detailed assessment of the components present in the O 1s sig-
nal, displayed in Fig. 5, together with the corresponding atomic fraction shown in
Table 3, allows to conclude that the underlying TiO2 (100) single crystalline surface
still exhibits the same OH:O2− ratio as the pristine crystalline surface (Table 1). A
slightly reduced value of the O/Ti ratio is seen in this case, which is attributed to the
displacement of adsorbed water molecules by NDCA.
XPS characterization reinforces the observation that NDCA molecules chemisorb
porly onto the TiO2 (100) single crystalline surfaces due to weak interactions occur-
ring between the hydroxyl-stabilized TiO2 surface and anchoring carboxylate groups.
Indeed, taking into account the presented data, no condensation between the latter
and hydroxyl groups present in the substrate surfaces can be detected. Consequently,
Table 3 Detailed Angle O /Ti O2− /Ti OH/O2− (H2 O,

composition of the O 1s (°) COOH)/O2−
element spectra of the NDCA
covered surface at varying 70 2.4 2.0 0.16 0.05
take-off angles (from [11]) 40 2.8 2.1 0.24 0.08
20 3.0 2.0 0.32 0.16
10 3.3 1.8 0.60 0.24
the ubiquitous presence of these hydroxyl groups, together with water adsorbate lay-
ers, on the TiO2 surface (prepared in ambient conditions) is tentatively proposed to
be responsible for the formation of the poorly packed and disordered NDCA layer
initially observed by AFM and XPS and lately supported by AFM nanoshaving. This
argument is additionally supported by Henderson et al. who reported the dissocia-
tion of water molecules on TiO2 (100) surfaces to give rise to two hydroxide groups
adsorbed onto the surface: the first one to Ti4+ adsorption sites, whilst the second
one would be bound at bridging O2− [24]. It has also been proposed that the adsorp-
tion of volatile molecules could also take place by forming Ti–O bonds [25]. The
latter, together with the above-mentioned hydroxide groups and the water adlayers,
would strongly inhibit the anchoring of carboxylate groups to this TiO2 (100) surface
prepared in ambient conditions.
Conclusions
A new methodology for the preparation of rutile TiO2 (100) crystalline surfaces
in water and oxygen partial pressures at high temperature is reported. Apart
from small amounts of carbon-based contamination bearing carboxylate moieties
(i.e. organocarboxilate adsorbates coming from the laboratory atmosphere), angle-
resolved XPS shows the presence of a hydroxyl layer terminating the single crystal
surface. Hydroxyl groups are proposed to chemisorb preferentially at defects present
on the TiO2 (100) surface lowering thus the surface energy.
The adsorption of NDCA molecules onto the as-prepared bare TiO2 (100) sur-
faces results in the displacement of the adventitious carbon layer typically present
at surfaces exposed to air and resulted in a noticeable rise in the contact angle from
18 ± 3° to 45 ± 3° [12]. The combination of angle-resolved-XPS and AFM nanoshav-
ing allows to conclude that a disordered adsorbate layer of NDCA molecules essen-
tially lying flat on the substrate terraces is formed (as opposed to the formation of
a self-assembled monolayer). Consequently, nanoshaving has been shown to be a
reliable method for the fundamental characterization of adsorbate layers. In the par-
ticular case of NDCA-coated TiO2 (100) substrates, nanoshaving unveiled disordered
organic layer exhibiting a fractional surface coverage consistent with a submonolayer.
The presence of terminating hydroxyl groups, together with water adlayers, on
the as-prepared TiO2 (100) crystalline surface strongly inhibits the formation of
well-defined tightly packed and ordered NDCA monolayers. Consequently, weak
interactions between the anchoring carboxylate groups and the hydroxyl-stabilized

TiO2 (100) terraces, namely hydrogen bridging, are proposed to be responsible for
the observed behaviour.
Nanoshaving and Nanografting of ODPA Monolayers

on Al2 O3 Surfaces [22]
The combination of nanografting and nanoshaving techniques can be considered

a valuable tool to assess the quality of self-assembled monolayers. The charac-
terization of a vast variety of spontaneously adsorbed molecules on noble metals
has been carried out by means of AFM-based nanografting over the last few years
[26–28]. In particular, the impact exerted by different distal functional groups and
chain lengths on frictional coefficients has been assessed by nanografting. In addi-
tion, the differential adsorption of thiol molecules by means of either nanografting
or self-assembly has been compared [27, 28]. Most importantly, it has been stated
that as a consequence of the reduced spatial confinement, fewer pinholes and defects
can be obtained in the grafted patches in comparison to those obtained in the outer
self-assembled molecule layer regions [28]. In this regard, nanografting appears as
a very reliable and useful technique for the characterization and modelling of the
molecular adsorption and self-assembly processes at the nanoscale. Indeed, when
the spontaneous chemisorption of certain molecules exhibiting enhanced affinities
for specific surfaces is considered (for instance aliphatic thiols on gold), then the
suitability of using in situ-AFM measurements for the monitoring of the monolayer
assembly decreases. In the following, nanografting and nanoshaving processes have
been carried out to characterize the adsorption of phosphonate-terminated aliphatic
molecules onto Al2 O3 (0001) single crystals. The study was supplemented with XPS
measurements of the surfaces.
High-resolution AFM images registered in both contact and AC mode for the
bare Al2 O3 single crystals measured in ambient conditions are displayed in Fig. 6.
The solvent-cleaned substrates exhibited a relatively smooth surface which turned
into characteristic atomically flat terraces after etching and thermal annealing. Sim-
ilar results to these presented in this chapter have been reported elsewhere [29, 30].
These terraces are in the range of ~1 μm wide. However, the methodology employed
for the preparation of this multistep terraced morphology brought about some inho-
mogeneities, even when analogue Al2 O3 (0001) substrates were submitted to identical
experimental conditions. These particular results can be summarized as follows: (i)
typical morphological features, involving multistep ~1 μm-wide atomically flat ter-
races, were obtained for all the samples measured, as can be seen in the topographical
AFM images depicted in Fig. 6a, c, e; however, (ii) noticeable heterogeneities were
then unveiled by both friction (Fig. 6b, f), and phase contrast images (Fig. 6d).
These results can be tentatively interpreted as follows. When working in ambient
conditions, water adlayers adsorbed onto the surface are expected to modify signifi-
Fig. 6 AFM images showing morphological differences and heterogeneities on Al2 O3 (0001) sur-
faces. a and c Topography images of typical atomically flat terraces. b Friction and d phase images
reveal different terminations on the same terrace. e and f Similarly prepared single crystals showing
domains (e topography image; f friction image). The measurements were performed under ambient
conditions. Reprinted from [22] with permission from Elsevier
cantly the tip-to-surface interaction contact forces. In this context, although the height
differences, which can be obtained from topographical AFM images by performing
cross section profiles, are in the range of ~100 pm, noticeable phase and friction
contrast showing well-defined domains can be observed in Fig. 6b, d, f. The latter
could then be attributed to the presence of water adsorbate layers on the crystalline
surfaces. Interestingly, large rounded and elongated domains seem to coexist with
smaller and amorphous islands (see Fig. 6e). Consequently, the presence of these
domains definitely accounts for a differential friction behaviour which is eventually
indicative of a different surface termination. However, AFM experiments carried out
in UHV at 140 °C showed the persistence of these friction-contrast domains even
at high temperature, i.e. presumably in the absence of physisorbed water [22]. The
origin of the heterogeneities revealed by phase and friction contrast AFM imaging
is unclear. In the following, fot the sake of simplification, the morphologies shown
in Fig. 6b and d will be identified as type 1, whilst those displayed in Fig. 6f will be
named type 2. It is worth noting that previous studies carried out onto Al2 O3 (0001)
single crystals in UHV conditions pointed out to two distinct surface terminations,
i.e. Al and O [31]. Additionally, AFM-based studies, also performed in UHV, have
demonstrated a hexagonal conformation for two layers of Al atoms for these crys-
talline facets [32]. However, in contrast to the surfaces obtained in UHV conditions,
single crystalline Al2 O3 (0001) substrates prepared in ambient experimental condi-
tions exhibit a differential surface composition since they are exposed to both oxygen
activity and water adlayers. Indeed, it has been widely stated that hydroxide-coated
alumina crystalline surfaces are the most stable configurations under ambient con-
ditions since hydroxylation is expected to decrease the surface energy of aluminium
oxide [33]. Thus, in the absence of water, Al and O surface terminations would be
expected. However, aluminium oxide surfaces are expected to suffer hydroxylation
in water-containing ambient condition as published elsewhere [29]. In fact, the exis-
tence of hydroxyl-stabilized Al2 O3 (0001) terraces in the alumina substrates etched
and annealed in ambient (water containing) conditions has been proved by XPS,
shown in Fig. 7.
Once the adsorption of octadecylphosphonic acid (ODPA) molecules (from
ethanol) on the as-treated Al2 O3 (0001) terraces (after etching and annealing in ambi-
ent conditions) has taken place, AFM nanoshaving was performed onto the ODPA-
modified alumina single crystal. In this context, AFM imaging carried out onto the
latter modified substrate and displayed in Fig. 8a shows the formation of a very
homogeneous and closely packed ODPA layer. A representative cross section profile
taken in the AFM image depicted in Fig. 8a point at two terraces, indicated with stars,
exhibiting a rougher surface, in contrast with the other much smoother surrounding
terraces. This fact has been tentatively attributed to weak interactions between the
phosphonate anchoring groups and the Al2 O3 (0001) terraces giving rise to a dis-
ordered and poorly bound ODPA layer. Conversely, a stronger interaction with the
Al2 O3 (0001) surface together with the formation of a compact and tightly packed
ODPA film on the smoother terraces is proposed.
Taking this fact into account, for the following an ODPA-modified Al2 O3 (0001)
substrate exhibiting the afore-mentioned two types of organic films (disordered and
Fig. 7 XPS measurements of the O 1s region of the Al2 O3 (0001) single crystal at a 70° and b 20°
take-off angle. The spectra were fitted with two components assigned to oxide (at lower binding
energy) and hydroxide species (at higher binding energy positions). A clear increase of the hydroxide
contribution was found for the spectrum acquired with a lower take-off angle, indicating that the
hydroxide lies on top of the surface. Reprinted from [22] with permission from Elsevier
compactly packed) is considered, as can be seen in the white rectangle area indicated
in Fig. 8b. By applying with the AFM tip a high enough loading force in contact mode
to the ODPA-modified aluminum oxide single crystal, the organic layer is completely
removed unveiling thus the underlying substrate surface, i.e. nanoshaving, see the
ploughed squared area in Fig. 8c. The as-detached ODPA molecules rapidly diffuses
to the bulk ethanolic solution and no readsorption is detected at all. Cross section
profiles carried out through the “shaved” and surrounding areas in the same terrace
allows to accurately quantify the thickness of the ODPA layer. Thus, the as-measured
thicknesses in both differentiated regions (1 and 2 as identified in Fig. 8b) reaches
a value of ~2.0 nm which is quite close to the theoretical length calculated for the
ODPA molecule. The latter is therefore indicative of ODPA monolayer film formation
in a slightly tilted standing-up configuration in the two different areas shown in
Fig. 8b. Most importantly, after successive AFM scanning on the same area, only
ODPA molecules strongly adsorbed on the ordered and well-packed domains on the
Al2 O3 (0001) terraces remain adsorbed, while those weakly adsorbed in disordered
ODPA regions are subsequently removed as can be observed in Fig. 8d. This result
hints at the fact that ODPA molecules can presumably bind strongly to just one single
type of surface termination. Conversely, physisorption is most likely to occur on the
other crystalline surface termination.
Nanografting experiments have been carried out on hexylphosphonic acid (HPA)-
modified Al2 O3 (0001) single crystals by using longer aliphatic chain ODPA
molecules. More stable self-assembled monolayers can be obtained for phosphonate-
terminated molecules incorporating longer aliphatic chain due to the enhanced inter-
molecular van der Waals interactions. After nanoshaving the squared area displayed
in Fig. 9a of an HPA-modified Al2 O3 (0001) in a 1 mM ODPA-containing ethanolic
solution, the grafting of ODPA molecules in the “shaved” area, where HPA molecules
have been desorbed by AFM ploughing, has taken place. The latter can be justified
in terms of the brighter squared area corresponding to higher regions observed in
Fig. 8 a AFM topography of ex-situ adsorbed ODPA on Al2 O3 (0001). Topography b before and
c after nanoshaving on an area containing two different surface terminations. d Same crystal after
two AFM scans. ODPA stays stable only on one type of surface termination. The measurements
were performed in ethanol. Reprinted from [22] with permission from Elsevier
Fig. 9 Nanografting on Al2 O3 single-crystal surfaces. a Topography and b friction images after
nanografting in the presence of ethanolic ODPA solution on the HPA-covered (0001) surface.
Reprinted from [22] with permission from Elsevier
Fig. 9a. Since both molecules, i.e. HPA and ODPA, are CH3 -terminated, no remark-
able differences could be found in the AFM friction image (see Fig. 9b). Cross
section profiles performed through the squared and surrounding areas exhibit a pos-
itive height difference of 0.8 nm which is slightly lower but reasonably consistent
with the difference between the theoretical lengths of HPA and ODPA [22].
The results of the afore-mentioned experiments accounts for the systematic char-
acterization of the adsorption processes and self-assembly kinetics of phosphonate-
terminated aliphatic molecules on model aluminum oxide crystalline surfaces. The
preparation (chemical etching and thermal annealing) of Al2 O3 (0001) single crys-
talline surfaces upon exposure to ambient conditions brought about surface hetero-
geneities corresponding to a differential surface termination. The latter determines
the nature of the bonding interaction between the adsorbed molecule and the alu-
minum oxide surface and, consequently, both the ordering and density of the pack-
ing arrangement into a film, as reliably demonstrated by nanoshaving. Additionally,
nanografting has been shown to be a useful and reliable technique for studying
both adsorption and self-assembly kinetics of phosphonate-based moieties at the
liquid/metal oxide interface.
Investigation of TiO2 –TiO2 -Contact Forces Under UHV

Conditions
Contact forces between micro- and nanoparticles can be accurately estimated by force
spectroscopy measurements using an atomic force microscope (AFM). As previously
stated, under ambient conditions particle-to-particle interactions are significantly
influenced by the formation of capillary forces. Indeed, Farshchi-Tabrizi et al. [7]
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W I N D S .
The Winds, different from our Quarter of the World, in these Voyages
are either peculiar to warm Latitudes; such are Trade-Winds, Land
and Sea Breezes; or to the Coast, Tornadoes, and Air-Mattans.
Trade-Winds are easterly, blow fresh night and day, all the Year,
and every where round the Globe; that Part of it I mean that we are
upon, the Ocean, whether Atlantick, Indian, or American: for the Soil
and Position of Lands, though the same Cause of them subsists
more powerfully, gives uncertain and various Deflections. They will
extend to 30°° of N. Latitude, when the Sun is on this side the
Equator, and as far S. when on the other; deflecting where he is
farthest off (here to the N. E. there to the S. E.) and always nearest
to the E. Point on the Equinoctial, or where he is vertical.
The general Causes assigned by the Ingenious for these
Phænomena, and with the greatest Probability of Truth, are;
First, the daily Rotation of the Earth Eastward upon its Axis,
whereby the Air or Wind (the enforced Stream of it) by this means
goes Westward in respect of the Superficies; and this is farther
countenanced in that these Winds are found only in the largest
Circles, where the diurnal Motion is swiftest; and also because they
blow as strong in the Night as Day; home, on the Coast of Brasil, as
near Guinea.
The second permanent Cause of this Effect, the ingenious Dr.
Halley ascribes to the Action of the Sun-beams upon the Air and
Water every day, considered together with the Nature of the Soil, and
Situation of the adjoining Continents.
The Sun heats and rarefies the Air exceedingly, in all Latitudes
within the Zodiack, (evident from the anhelous Condition it subjects
most Animals to in Calms) and therefore the Air from Latitudes more
without his Influence (as more ponderous) presses in, to restore the
Equilibrium: and to follow the Sun, must come from the Eastward.
The westerly Winds that restore this Balance, from Latitudes beyond
the Tropicks, would, I fancy, be as constant, and keep a Circulation,
were the whole a Globe of Waters: As it is, they are from 30 to 60°°,
abundantly the most predominant, with a Deviation to N. or S. on
various Accidents: blow with more force, because, among other
Reasons, the Equilibrium is restored to a greater from a lesser
Circle; and as it were to confirm this, are received into the Trade-
wind, with a Deflection of N. E. or more northward at the Point of
reception.
On the Coast of Guinea, North of the Equinoctial, the true Winds
are westerly, keeping a Track with the Shore, where it trenches all
eastward. From the River Gabon again, under the Line, the Land
stretches to the Southward, and, exactly answerable thereto, the
Winds wheel from S. E. to S. by E. to keep nigh a Parallel with it; in
both, the Shore seems to deflect the true Trade, in the same manner
Capes do Tides or Currents, and obliges it, like them, on that Point
where they have the freest Passage. If at any particular Seasons (as
in the Rains is remarked) the Winds become more southerly, and set
full upon the Shore, they are weak; and as the Sun is at such time on
this side the Equinoctial, it is probably to restore an Equilibrium to
that Air at land, more rarefied from a stronger and more reflected
Heat.
I shall give two or three other Remarks on Trade-winds, proper,
tho’ made at other Periods of the Voyage.
1. You must be distant from the Influence of Land to Windward,
before the Trade blows true and fresh, (from this Coast we may
suppose twenty or thirty Leagues) and then a Ship bound to America
will make a constant and smooth Run of forty or fifty Leagues every
twenty-four Hours. And as there are no Storms, vast numbers of
flying Fish sporting near the Ship, (found every where within the
Verge of these Winds, and no where else that ever I saw,) Bonetoes
pursuing them; with Birds of various sorts, Garnets, Boobys, Tropick-
Birds, and Sheerwaters, it makes a very delightful sailing.
2. Although the N. E. and S. E. Trade-Winds on this and that side
the Line, do not blow adverse, yet by approaching to it, are in my
Thoughts, the Occasion of becalming the Latitudes between 4 and
12° N, the Point of Contest; as we found, and will be hereafter
remarked in our Passage from Brasil to the West-Indies, in July and
August: and this I think, First, because the East southerly Trade is
known ordinarily to extend E. S. E. to 4° of Northern Latitude: and
consequently, as the East northerly is bounded a little nearer or
further from the Equinoctial, as is the Station of the Sun; Calms and
small Breezes, the Attendant of them, may vary a little, yet they will
always happen about these Latitudes, and near the windward
Shores be attended with Thunder, Lightning, and perpetual Rains.
Secondly, all Ships actually find this in their Passage from Guinea to
the West-Indies in any Month, or from England thither; the true Trade
decreasing as they approach those Latitudes, and up between Cape
Verd and the Islands, those Calms by all our Navigators are said to
be as constantly attended with Rains and Thunder.
Thirdly, Because the same thing happens at the Commencement
of the Trade, from the variable Winds in 27 or 28°° of Northern
Latitude, sooner or later as I observed is the Station of the Sun:
From all which I would infer, that from Guinea these calm Latitudes
are easier passed, not nigh, but within 100 Leagues of the Continent
of Africa, and at America not to get into them till a Ship has nigh run
her Distance; for the Land, I think, either to Windward or Leeward
does give a better Advantage to the Breezes, than nearer or more
remote: Ships from England do not want this Caution so much,
because the N. E. Trade does not fail till a little beyond the Parallel of
Barbadoes, the Southermost of our Islands.
Land and Sea-Breezes are Gales of no great Extent, the former
much fainter and inconstant will blow off an Island to a Roadsted, be
on which side of it you will, but whether at the same time or no, or
now here, now there, I am not experienced enough to say, tho’ their
Weakness and Inconstancy makes either way defensible.—They are
found at all shores within or near the Tropicks, the Sea-breeze
coming in about ten in the morning, fresh and sweet, enlivening
every thing. The Land-breeze when it does succeed, is at the same
distance from Sun-set or later, small, sultry, and stinking, especially
when from Rivers whose Banks are pestered with rotten Mangroves,
stagnating Waters, &c.
They seem to arise entirely from the Heat of the Sun-beams: That
the Air is more rarified by their Reflections on the solid Body of the
Earth than on a fluid, is certain; therefore till their rarified Air, made
so by three or four hours Sun, is brought to an Equilibrium, the
Breezes must be from the Sea at all parts of the Coast, because at
all parts, the same Cause is operating. And if this Rarefaction is
limited by a determined heighth of the Atmosphere, the Sea-breezes
that are to fill up the Vacuities will last a determined time only; two,
three, or more hours: this is fact, but whether properly solved, must
be submitted. Of affinity with this are the frequent Breezes we find
with meridian Suns at shores, even to the Latitude of England, tho’
very still before and after. Again, the Land-breezes which succeed at
night when the Sun has lost it’s Power, seem by their Weakness to
be the return of Air heaped up by the preceding day’s Heat, like
other Fluids when higher or fuller from any Cause (in one part than
another) of course has it’s reflux to make an even Surface.
Tornadoes, by the Spaniard called Travadoes, are in no part of the
World so frequent as at Guinea. They are fierce and violent Gusts of
Wind that give warning for some hours by a gradual lowering and
blackening of the Sky to Windward whence they come, accompanied
with Darkness, terrible Shocks of Thunder and Lightning, and end in
Rains and Calm. They are always off shore, between the N. and N.
E. here, and more Easterly at the Bites of Benin, Calabar, and Cape
Lopez; but although they are attended with this favourable Property
of blowing from the shore, and last only three or four hours, yet
Ships immediately at the appearance of them furl all their Sails and
drive before the Wind.
We have sometimes met with these Tornadoes two in a day, often
one; and to shew within what a narrow Compass their effects are,
Ships have felt one, when others at ten Leagues distance have
known nothing: Nay, at Anamaboo (3 or 4 Leagues off) they have
had serene Weather while we have suffered under a Tornado in
Cape Corso Road. And vice versa. A Proof of what Naturalists
conjecture, that no Thunder is heard above 30 Miles; in these
Storms it seems to be very near, one we felt the Afternoon of taking
Roberts the Pyrate, that seemed like the ratling of 10000 small Arms
within three yards of our Heads; it split our Maintop-Mast, and ended
as usual in excessive Showers, and then calm; the nearness is
judged by the Sound instantly following the Flash. Lightning is
common here at other times, especially with the shutting in of
Evening, and flashes perpendicularly as well as horizontally.
Both arise from a plenty of nitrous and sulphurous Exhalations that
make a Compound like Gun-powder, set on fire in the Air; and if the
Clouds that retain them be compact, and their heterogeneous
Contents strong, various, and unequal, then like a Cannon in
proportion to these, the disjection is with more or less Violence,
producing Thunder, which as with a [32]Shot has frequently split the
Masts of Ships; and strengthens the above Observation of their
being discharged near hand; because if at any considerable
distance, they would spread in the Explosion, and lose their Force. It
furnishes also another, viz. That neither Thunder nor Lightning can
be felt or heard far from shores; Winds may impel such Exhalations
something, but at a hundred Leagues from any Land the
Appearance must be rare and uncommon, because the matter of
their Compound cannot be collected there.
Air-mattans, or Harmatans, are impetuous Gales of Wind from the
Eastern Quarter about Midsummer and Christmas; they are attended
with Fogs, last three or four hours, (seldom with Thunder or
Lightning, as the Tornados) and cease with the Rain; are very dry,
shriveling up Paper, Parchment, or Pannels of Escruitores like a Fire.
They reach sometimes this Gold Coast, but are frequentest and in a
manner peculiar to the Bite of Benin, named so some think from Aer
Montain, respecting whence they come; or by others Mattan, the
Negrish Word for a pair of Bellows, which they having seen,
compare this Wind to.
The G U I N E A Trade.
An extensive Trade, in a moral Sense, is an extensive Evil, obvious
to those who can see how Fraud, Thieving, and Executions have
kept pace with it. The great Excess in Branches feeding Pride and
Luxury, are an Oppression on the Publick; and the Peculiarity of it in
this, and the Settlement of Colonies are Infringements on the Peace
and Happiness of Mankind.
By discoursing on this particular Branch, I do not pretend to a
Sufficiency of giving full Directions; the Natives Alteration and
Diversity of Taste are Obstacles with the most experienced: It’s only
within my Design to give a general Insight to such as are Strangers,
and a Rule to improve upon by such as are not.
We may for this end divide Guinea into a windward Coast, the
Gold Coast, and the Bay, a Tract of 6 or 700 Leagues from the River
Gambia, in 13°° N. to Angola, about 9 or 10°° S. The Portuguese
were the first Europeans that settled and built Forts here, tho’ now
the least concerned, paying their Tribute to the Dutch for Leave:
What remains of theirs is to the Southward on the River Congo at
Loango de St. Paul, and the Islands, where they keep Priests to
teach their Language to the Natives, and baptize without making
Christians.
1. In the windward Coast, Gambia, Sierraleon, and Sherbro Rivers
may be reckoned chief; the African Company having Factors and
Settlements there. Less noted, but more frequented by private Ships
in this part of Guinea, are Cape Mont, and Montzerado, Sesthos
River, Capes Palmas, Apollonia, and Tres Puntas. A number of
others intervene, of more or less Trade; which it is their Custom to
signify at the sight of any Ship by a Smoke, and is always looked on
as an Invitation to Trade; but as each is alterable among them from
the Chance of War, the Omission shews they decline it, or are out of
Stock.
This Change of Circumstance found on different Voyages,
proceeds from weak and bad Governments among themselves,
every Town having their own Cabiceers or ruling Men, (or it may be
three or four in Confederacy) all so jealous of the others Panyarring,
that they never care to walk even a mile or two from home without
Fire-Arms; each knows it is their Villanies and Robberies upon one
another that enables them to carry on a Slave-trade with Europeans;
and as Strength fluctuates, it is not unfrequent for him who sells you
Slaves to-day, to be a few days hence sold himself at some
neighbouring Town; this I have known.
The same way of reasoning answers for the Panyarrs and
Murders so frequently between them and us, and never that I heard
with the French or Portuguese. For if any of our Ships from Bristol or
Liverpool play tricks, and under pretence of Traffick seize and carry
away such of them as come on board, and trust themselves on that
Confidence, the Friends and Relations never fail with the first
Opportunity to revenge it; they never consider the Innocence of who
comes next, but as Relations in Colour, Panyarr the Boat’s Crews
who trust themselves foolishly on shore, and now and then by
dissembling a Friendship, have come on board, surprized and
murdered a whole Ship’s Company. Captain Piercy’s Lieutenant was
killed on shore on some such Pretence, or because he had a good
Suit of Cloaths, or both. Captain Canning of the Dove Brigantine
1732, was cut off by the Natives of Grand Bassau from an
Inadvertency; first, of tempting the Negroes with the sight of a fine
Cargo, and then by trusting the Mate Mr. Tho. Coote on shore; the
one prompted them to rob, and the other was an Hostage for their
Security, they ventured off in their Canoos and murdered all the
Company under the Conduct of a Fellow they called Thomas Grey,
who run the Vessel in shore; the Mate remained with them unhurt,
about sixteen days, and was then redeemed by Captain Wheeler for
17 Pounds worth of Goods, which as an Encouragement to the
Service, he was suffered to repay at London. His Food during the
stay, was Indian Corn, Rice, Snails and Monkeys; the last they shoot
as often as they want, in the Woods, and after the Guts are taken
out, singe the Hair off, and then boil it in the Skin. He saw no other
Flesh in this part of the Country, excepting a few Fowls, tho’ he was
up it above twelve miles.
2. The Gold Coast is the middle and smallest part of the Division,
stretching from Axiem a Dutch Settlement, to near the River Volta,
an extent of 70 or 80 Leagues, but of more consequence than the
others, in respect to our’s and the Dutch Company’s Forts, who
together command the greatest part of it. There is one Danish Fort at
Accra indeed, (the Leewardmost of our Settlements) but in a
decaying State, and will probably (as that of the Brandenburghers at
Cape Tres Puntas) be relinquished in a little time.
Our Company’s principal Fort is at Cape Corso. That of the Dutch,
two or three Leagues above, called Des Minas or St. George de
Elmina; each has other little ones up and down this Coast, to gather
in the Trade that centers for the respective Companies, at one or
other of the aforesaid larger Forts.
The African Company was erected under the Duke of York in K.
Charles II’s Time, and therefore Royal; the Epithet being still
retained, tho’ that Prince’s Superstition, and Thirst after Power, have
long since justly banish’d him the Realm.
In it’s first flourishing Condition, it was allowed by authentick
Accounts to have gained annually to England 900,000l. whereof in
Teeth, Camwood, Wax and Gold, was only 100,000l. and the rest in
Slaves; which in the Infancy of their Trade were in very great
demand over all the American Plantations to supply their own wants,
and carry on a clandestine Commerce with the Spanish West-Indies.
On Computation, Barbadoes wanted annually 4000 Negroes,
Jamaica 10000, Leeward Islands 6000; and because the Company
(’twas complained by such as wished them ill Success) could not
supply this Number, having only imported 46396 Slaves between the
years 1680 and 1688; Interlopers crept in, and contended for a
Share; which the Company represented as contrary to the Privileges
of their Patent, and withal, that the Accusation was groundless and
unjust, because they did supply enough for demand, and maintained
Forts and Garisons at a great Charge, for awing and subjecting the
Natives to trade, and maintaining an Industry equal to the Dutch,
without which it was plain to all impartial Considerers, it would be but
very difficultly carried on. However, their Adversaries, after some
years of grumbling, obtained an Act of Parliament 1697, whereby
private Traders for making good this deficiency of Slaves, should
have Liberty of Trade, allowing the Company 10 per Cent. towards
defraying their extraordinary Expence.
From this time the Company more visibly decayed, insomuch that
in eight following years they only imported to the West-Indies 17760
Slaves; and the separate Traders in that time 71268.
Their 10 per Cent. in the first ten years amounted to 87465l. and
therefore finding their Trade under great disadvantages with these
new Inmates, they resolved to make the best shares they could in
this Money, by lessening their Expence about the Forts. They
accordingly withdrew all Supplies from their Garisons, leaving them
to subsist by their own Management or starve. Gambia Fort having
only twelve men, was taken by a Privateer of eight Guns in 1709,
Sierraleon thirteen men, Sherbro four, and these not of any Charge
to the Company, but were possessed by such, who having a long
time resided in their Service, by help of those Fortifications were
capable to do something for themselves, and so the private Traders
by degrees got entirely quit of their Impost; the reason in a manner
ceasing, for which it was at first allowed.
About 1719, their Affairs seemed to revive again, under the
Auspices of the Duke of Chandois, who became a very considerable
Proprietor in their Stock, and promised from his Figure and Interest a
Renewal of those Privileges that had depressed them; their
Objections ceasing, (the number demanded being now very short of
what it was formerly.) More Ships were imployed than for many
years past, but whether it were their too large Expence, or
Corruption of their chief Officers, who too often in Companys think
they are sent abroad purely for their own Service, or both; they soon
felt that without a separate Act they were uncapable of contending
with private Traders, and every year more and more explaining their
Inability, they applied to Parliament, and now support their Forts by
an annual Allowance from the Government, of 10000l.
Those who are the Favourers of Companies suggest, that if the
Trade must be allowed, and the Christian Scheme of enlarging the
Flock cannot well be carried on without it, that then it seems
necessary and better for the Publick that some rich and powerful Set
of Men should have such exclusive Powers to encourage and enable
the subsisting of Forts and Garisons, to awe the Natives and
preserve the Trade from being engrossed by our dangerous Rivals
here, the Dutch; which, as we relinquish, falls an acquisition to them,
and renders all precarious; they could also bring (as an exclusive
Company) foreign Markets to their own Price.
The Company’s Trade wanting that Encouragement, every year
grows worse; buying dearer than in times past on the Coast, and
selling cheaper in the West-Indies; the reason at Guinea, is a greater
Scarcity of Slaves, and an improved Knowledge in the trading
Negroes who dispose of them; and at the West-Indies it is the
Demand failing, more disadvantageously still for them, because
separate Traders are not under the delays they are subject to: They
take the whole Coast in their way, while the other is consigned to the
Governour, and can afford to undersel their Goods (necessary
Requisites for Dispatch and Success) because they stand exempt
from all Coast-Charges. On the other side, our Colonies are now
pretty well glutted with Slaves, and their Call consequently not nigh
so large: 2000 in a year perhaps furnishes all our Plantations, and
tho’ more are imported, it is in order to transport them again to the
Spanish West-Indies, where tho’ the Assiento Ships are of late years
only indulged by Treaty, all others being liable to Confiscation, and
the People to Slavery if taken by the Spanish Guard le Costa; yet the
Prospect of Gain inciting, they still find means to continue on, and
maintain a forcible Traffick for them, under the Protection of their
Guns. This clandestine Method, by the way, hurts the South-Sea
Company, beating down the Price of their Slaves, who cannot so
well afford it, because bought, and brought there at a greater
Charge.
The third part of our Division is the Bay of Guinea, which takes in
Whydah, Benin, Callabar, &c. to Congo and Angola in 8°° S. In this
Extent Whydah is principal, there being more Slaves exported from
that place before the late Conquest of it by the King of Dauhomay,
than from all the rest of the Coast together, the Europeans being
said in some years to have carried off 20000; but more of this by and
by. I shall only observe, that as this part abounds more with Slaves,
the other does with Gold, and the windward Coast with Ivory.
I now proceed to our Method of Trade, and shall sum the Rules of
it up, under the head of Interlopers. Private trading Ships bring two
or three Boats with them upon this Coast for Dispatch, and while the
Mates go away in them with a proper Parcel of Goods, and
Instructions into the Rivers and By-places, the Ship is making good
her Trade at others near hand.
The Success of a Voyage depends first, on the well sorting, and
on the well timing of a Cargo. Secondly, in a Knowledge of the
places of Trade, what, and how much may be expected every where.
Thirdly, in dramming well with English Spirits, and conforming to the
Humours of the Negroes. Fourthly, in timely furnishing proper Food
for the Slaves. Fifthly, in Dispatch; and Lastly, the good Order and
Management of Slaves when on board; of each, a Word or two.
First, on the Timing of a Cargo: This depends at several places
much on Chance, from the fanciful and various Humours of the
Negroes, who make great demands one Voyage for a Commodity,
that perhaps they reject next, and is in part to be remedied either by
making the things they itch after, to pass off those they have not so
much mind to, or by such a continual Traffick and Correspondence
on the Coast, as may furnish the Owner from time to time with quick
Intelligence, to be done only by great Merchants, who can keep
imployed a number of Ships, that like a Thread unites them in a
Knowledge of their Demands, and a readier Supply for them, as well
as dispatch for their Master’s Interest, by putting the Purchases of
two or three Ships into one. The late Mr. Humphry Morrice was the
greatest private Trader this way, and unless Providence had fixed a
Curse upon it, he must have gained exceedingly.
Secondly, Of the Sorting, this may be observed in general; That
the Windward and Leeward Parts of the Coast are as opposite in
their Demands, as is their distance. Iron Bars, which are not asked
for to Leeward, are a substantial Part of Windward Cargoes.
Crystals, Orangos, Corals, and Brass-mounted Cutlasses are almost
peculiar to the Windward Coast;—as are brass Pans from Rio
Sesthos to Apollonia.—Cowreys (or Bouges) at Whydah.—Copper
and Iron Bars at Callabar;—but Arms, Gun-powder, Tallow, old
Sheets, Cottons of all the various Denominations, and English Spirits
are every where called for. Sealing-wax, and Pipes, are necessary in
small Quantities, they serve for Dashees (Presents) and a ready
Purchase for Fish, a Goat, Kid, or a Fowl.
To be more particular, here follows an Invoyce bought at London
about the year 1721.
A G U I N E A Cargo.
l. s. d. l. s. d.
10 Cotton Ramalls at 0 11 0 5 10 0
10 Silk Do 1 00 0 10 00 0
20 Herba-longees 0 10 0 10 00 0
20 Photees 0 17 6 17 10 0
30 Tapseils 0 12 0 18 00 0
20 Blue swaft Bafts 1 02 0 22 00 0
20 Chintz 0 12 6 12 10 0
50 Nichanees 0 13 0 32 10 0
176 Blue Paper Sletias 0 7 6 66 00 0
650 Crystal Beads No 221 per Mill. 2 00 0 13 00 0
2500 Do — No 30 2 12 0 6 10 —
4500 Do — No 36 2 18 0 13 01 0
2000 Rangos per Cwt. 0 11 0 11 00 0
4 Cases and Chests — — — 1 15 0
Charges and Entry at Custom-house — — — 3 12 6
Ct. q. l.
20 Brass Kettles qt. 2 0 02
28 Do 2 0 04
25 Do 2 0 06
251 Guinea Pans 3 0 18
-------------
9 1 02
per Cwt. 7l. 7s. 0d. 68 02 5
-------------
311 00 11
4 Casks 1 03 00
20 Chests of old Sheets each qt. 65,
0 1 10½ 121 17 06
at
130 2lb. Guinea Basins.
73 3 — Do
13 4 — Do
In all 4Cwt. 1q. 11l. 18 04 09
Box of Scales, Weights and blue
— 19 00
Pans.
Cartage, Portage, Wharfage, &c. 4 10 00
84 Quart Tankards at 2s. 2d. 9 02 00
96 Pint Do at 1 8 8 00 00
A Cask — 14 09
11 Groce of slope-pointed Knives at
14 06 00
1l. 6s.
200 Blue Ranters at 0 08 00 80 00 00
50 Narrow green Do 0 08 00 20 00 00
50 Broad blue Do 0 11 06 28 15 00
25 Says at 1 15 06 44 09 06
8 Cases with Carriage 2 10 06
150 Trading Guns at 0 08 03 61 17 06
50 Do dock Locks 0 08 06 21 05 00
150 Cags 0 00 07 02 10 06
21 Cwt. Tallow 2 01 00 43 01 00
For melting and putting up per Cwt. — 00 02 2 03 00
Cartage, and 10 large Cags — 00 11 00 16 08
-------------
797 06 07
35 Small Cags at 0 00 08 1 03 04
10 Barrels of Powder 3 05 00 32 10 00
Wateridge and shifting the Powder 00 08 06
50 Wickered Bottles 0 03 02 9 03 04
172 Gall. malt Spirits 0 02 00 17 04 00
40 Cases of Spirits 0 07 00 14 00 00
Freight of a Vessel to Portsmouth 5 10 00
Expences and Postage of Letters 0 11 00
Commission at 2½ per Cent. 22 03 03
-------------
900 00 00
10 Cwt. of Cowrys at 5l. 50 00 00
-------------
Total 950 00 00
I was but a young Trader, and could not find out till I came upon
the Coast, that this Cargo was ill sorted. At the first place we touched
(Sierraleon) where commonly may be got twenty or thirty as good
Slaves as any upon the Coast, I found I had neither Cutlasses, iron
Bars, a better sort of Fire-Arms, Malt, and other strong Liquors, the
delight of those Traders. At none of the others, quite down to the
Gold Coast, were many considerable Articles of my Invoyce ever
asked for; so that I was forced to make friends with the Factorys, and
exchange at such a loss, that had it not been for the small Wages
our Ship was at, and some lucky hits, the Owners must have
suffered much; but to give an Insight.
The Sale of Goods.

At Sierraleon.
Gold Bars.
1 Piece of Planes 10
7 77lb. Kettles 26
3 Pieces of Chintz 12
1 Piece of Handkerchief Stuff 2
---
The Price of a Woman Slave 50
7 50lb. Kettles 20
5 Pieces of Brawls 10
1 Piece of Ramal 4
1 Bar of Iron 1
---
The Price of a Boy Slave 35
At Apollonia.
Accys.
2 Photees 14
2 Cotton Ramals 8
1 Piece Longee 4
2 Sletias 5
7 Sheets 7
32 Brass Pans 32
---
A Man Slave 70
3 Photees 21
41 Sheets 41
2 Longees 8
---
A Man Slave 70
At Gambia.
Gold Bars.
9 Gallons of Brandy 9
6 Bars of Iron 6
2 Small Guns 10
1 Cag of Powder 10
2 Strings of Pacato Beads 2
1 Paper Sletia 3
---
A Woman Slave 40
At Assinee.
8 Trading Guns 32
1 Wicker Bottle 4
2 Cases of Spirits 6
28 Sheets 28
---
A Man Slave 70
At Anamaboo and Cape Palmas.

Accys.
A Cag of Tallow 2½
A quart Pewter Tankard 1
A Pint Do ½
4lb. Pewter Basin 1
2lb. Pewter Basin ½
Sealing-Wax 3
A qr. Barrel of Powder 8
A gallon Cag of Musket-Shot 6
A gallon Cag of small Shot 8
At Whydah,
Cowrys sell per Cwt.—— 12l. 10s. or in their
way of reckoning, 10 grand Quibesses.
At Angola, the Duties are about 100l. Sterl.
every Ship; and Goods sell, viz.
Pieces.
A Gun 1
A Cag of Powder 1
A deep blue Baft 3
A Culgee 3
A Tapseil 2
A Nicanee 2
A Cutchalee 1½
A red Chintz 1½
A Bundle of Anabasses qt. 10lb. 1
10 Brass Pans small and large 1
4 2lb. Pewter Basins 1
1½ Case of Spirits 1
A whole Case Do 1½
4 Cutlasses 1
A Guinea Stuff ½
2 Bunches of Beads 1
4 King’s Cloths 1
4 Looking-Glasses 1
10 Pint Mugs 1
A Brawl ½
9 Foot of black Bays 1
16 Inches of Scarlet Cloth 1
16 Do of blue Cloth 1
1 Photee 2
1 Pair Cotton Ramal 1½
As I propos’d only a general View of the Trade, I have pointed out

here the best I could, what Goods are asked for, the Price, and at
some places, the Proportion; the Slaves selling at a Medium of 15l. a
Man, and 12l. a Woman; a Gun and Barrel of Powder being always
parts of the Truck (at Cabenda) for a Slave. They have Canoos
there, will carry 200 Men; matted Sails to them, and Cordage twisted
from a wild Vine that grows in plenty about the Country; with these
they pass frequently from Congo to Loango. A Slave-Ship in the
former River would intercept much of the Trade to Cabenda and
Angola: The Duties are easy with the King of Soni, and the Harmony
they live in with a few defenceless Portuguese Missionaries, shews
they are a peaceable People.
A Second Requisite for Success in this Trade, is an acquaintance
with the Places, what may be expected at them, either as to the
Manner of Trading, bold or fearful of one another, and the Number of
Slaves they are able to bring.
Where the Company’s Factors are settled, as at Gambia, and
along the greatest part of the Gold Coast, they influence the Trade
something against private Ships; so also at Sierraleon some
separate Traders live, who voyage it with Boats into the adjacent
Rivers, and most of what a Ship can purchase, is thro’ their hands;
but those from London seldom strike higher upon the Coast than
Cape Mount, Montzerado, and Junk, falling from thence down to
Leeward; many of the places in their Course being rendered
dangerous, from the Tricks and Panyarrs the Traders have first
practised upon the Negroes; a mutual Jealousy now keeping each
side very watchful against Violence. We trade on board the Ship,
often keeping our Sailors in close quarters abaft, because few: while
the Slaves are viewing and contracting for at the fore part; at night
also keeping a good Watch, some of these Negroes attempting now
and then to steal with their Canoos athwart your Hawse, and cut the
Cable. Captain Cummin at Whydah, they stranded 1734.
They again, are as often diffident of coming nigh us, and will play
for hours together in their Canoos about the Ship, before they dare
venture. In this windward part, I have before observed, they have a
superstitious Custom, of dropping with their Finger a drop of Sea-
Water in their Eye, which they are pleased when answered in, and
passes for an Engagement of Peace and Security; and yet after all
this Ceremony, they will sometimes return to shore: If hardy enough
to come on board, they appear all the time shy and frightned, and
from the least appearance of a Panyarr, jump all over board.
Downwards to Bassam, Assinee, Jaquelahou, Cape le Hou, Jaque a
Jaques, Cape Apollonia, and Three Points, or where they have
possibly gained a Knowledge of the English Factorys, there is a
better Understanding and Security: These are places that sell off a
number of Slaves, managed however wholly on board the Ships who
anchor before the Town, hoist their Ensign, and fire a Gun: Or when
the Natives seem timorous, do it by their Boats coasting along the
Beach, and pay at some of them a small Duty to the chief Cabiceers.
Thirdly, To give dispatch, cajole the Traders with Dashees of
Brandy, and tell them, you cannot possibly stay above a day or two,
and that on their account. To a Country-Man, if he joins where there
is prospect of Goodee Trade, you are to form some Story that may
carry him farther to Leeward if possible, (two or three Leagues will
hinder his doing you any Damage for that Voyage.) The Lye did me
most Service, and for which I had the Merchant’s Dispensation, was
informing my good Friend that at Cobelahou they had taken a great
number of Captives, and that Captain —— had got his Freight there
in ten days: this I did with an air of Diffidence, to make the greater
Impression, and at the same time dashee’d his Negro Friends to go
on board and back it. If on better Intelligence such like Story should
not take, and he resolves to stay and share, your Reputation is
secured by the diffidence of your Report, and you must resolve with
him now upon a Price in your Slaves, not to outbid one another; but
at the same time make as strong a Resolution not to observe it. And
here the Master has room to display his talent, the frequency of the
Trick having made all very cautious and diffident.
When a Ship has gathered up all this Trade, she makes up the
deficiency of her Freight at Anamaboo, three Leagues below Cape
Corso, where they constantly stop, and are sometimes two or three
Months in finishing. It is a place of very considerable Trade in itself;
and besides, the Company have a House and Factor, keeping
always a number of Slaves against those demands of the
Interlopers, who, they are sensible, want dispatch, and therefore
make them pay a higher Price for it than any where on the whole
Coast; selling at six Ounces and a half a Slave (in exchange for
Goods) tho’ the poor Creatures look as meagre and thin as their
Writers.
If the Company should want rather to buy than sell, as is
sometimes the case, and fits both; then such a difference is paid by
the General, as shall make it worth the Ship’s time to go to
Windward again.
Hence I make this deduction, that if the Adventurers Stock be
small, only sufficient to employ one Vessel, to have her a Sloop;
because less hazard is run in lengthning out time, which subjects to
Sickness and Mortality among the Slaves; saves the aggregate
Charge of supporting them and a Ship’s Company, and likewise such
a Vessel will have less remains of Cargo, after her Slaving is
compleated; what is left, usually going off to the trading Cabiceers
and Factories at a low Price, or what is worse, kept on board and
spoiled.
Contrarily, great Traders who can imploy many Ships, obviate in a
great measure such Inconveniencies: They put the Trade of two or
three Ships into one at Anamaboo, (the largest and most
chargeable) and with the conjunction of their remains, go to
Windward, and begin anew.
Fourthly, giving way to the ridiculous Humours and Gestures of the
trading Negroes, is no small artifice for Success. If you look strange
and are niggardly of your Drams, you frighten him; Sambo is gone,
he never cares to treat with dry Lips, and as the Expence is in
English Spirits of two Shillings a Gallon, brought partly for that
purpose; the good Humour it brings them into, is found discounted in
the Sale of Goods.
A fifth Article, is the wholesome Victualling, and Management of
Slaves on board.
The common, cheapest, and most commodious Diet, is with
Vegetables, Horse-Beans, Rice, Indian Corn, and Farine, the former,
Ships bring with them out of England; Rice, they meet to Windward,
about Sesthos; Indian Corn, at Momford, Anamaboo, &c. and further
Supplies of them, or Farine, at the Islands of St. Thomas, and

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PDF Particles in Contact Micro Mechanics Micro Process Dynamics and Particle Collective Sergiy Antonyuk Ebook Full Chapter

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Particles in Contact Micro Mechanics

Micro Process Dynamics and Particle

Nonlinear Differential Equations in Micro/Nano

Micro-computed Tomography (micro-CT) in Medicine and

Being Feared The Micro Dynamics of Fear and Insecurity

Micro-blogging Memories: Weibo and Collective

Microfluidics: Modeling, Mechanics and Mathematics. A

Modelling and Mechanics of Carbon-Based Nanostructured

Micro Frontends in Action 1st Edition Michael Geers

Micro Frontends in Action 1st Edition Michael Geers

ISBN 978-3-030-15898-9 ISBN 978-3-030-15899-6 (eBook)

The properties and behaviour of particulate products, such as powder materials,

Kaiserslautern, Germany Sergiy Antonyuk

Analysis of Adsorbates and Interfacial Forces at Metal Oxide

Capillary Interaction in Wet Granular Assemblies: Part 2 . . . . . . . . . . 277

Structure of Sheared Cohesive Granular Bulk . . . . . . . . . . . . . . . . . . . . 607

A. G. Orive, C. Kunze, B. Torun, T. de los Arcos and G. Grundmeier

A. G. Orive · C. Kunze · B. Torun · T. de los Arcos · G. Grundmeier (B)

© Springer Nature Switzerland AG 2019 1

Materials and Methods

Materials and Surface Preparation

Materials and Chemicals

Preparation of Rutile TiO2 (110) and (110) Single Crystalline Surfaces

conventional 1 × 3 superstructure was obtained in the LEED pattern registered for

Preparation of Al2 O3 (0001) and (11–20) Single Crystals [11]

Fig. 1 AFM topography

Adsorption of Organic Monolayers on TiO2 and Al2 O3 Single Crystalline

Ambient Pressure AFM

TiO2 Coated AFM-Tips

Macromolecular Modification of AFM Tips

The solvent cleaned gold-coated cantilevers were introduced into a 1 mM A-Hydroxy-

The solvent cleaned gold-coated cantilevers were introduced into a 1 mM

The solvent cleaned gold-coated cantilevers were introduced into a 1 mM α-Methoxy-

XPS measurements were performed in an Omicron ESCA+ System (Omicron

Analysis of Disordered Molecular Adsorbates by Means

The molecular adsorbate formation of alkanehydroxamic and carboxylic acids on

The topographical features exhibited by adsorption of NDCA molecules onto

Table 1 Surface composition Angle (°) O 1s (at.–%) Ti 2p 3/2 C 1s (at.–%)

Table 2 Surface composition Angle (°) O 1s (at.–%) Ti 2p 3/2 C 1s (at.–%)

hydroxide-terminated surface. Consequently, it could be concluded that a layer of

Fig. 5 O 1s spectra of the

The as-prepared NDCA adsorbate film exhibits the characteristic C 1s spectrum

Table 3 Detailed Angle O /Ti O2− /Ti OH/O2− (H2 O,

interactions between the anchoring carboxylate groups and the hydroxyl-stabilized

Nanoshaving and Nanografting of ODPA Monolayers

The combination of nanografting and nanoshaving techniques can be considered

Investigation of TiO2 –TiO2 -Contact Forces Under UHV

The Sale of Goods.

At Anamaboo and Cape Palmas.

As I propos’d only a general View of the Trade, I have pointed out

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