Structure of the in situ produced

polyethylene based composites

modified with multi-walled carbon
nanotubes: In situ synchrotron X-ray
diffraction and differential scanning
calorimetry study Coll.
Visit to download the full and correct content document:
https://ebookmass.com/product/structure-of-the-in-situ-produced-polyethylene-based-
composites-modified-with-multi-walled-carbon-nanotubes-in-situ-synchrotron-x-ray-dif
fraction-and-differential-scanning-calorimetry-study-coll/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

In-situ growth of CoP wrapped by carbon nanoarray-like

architecture onto nitrogen-doped Ti3C2 Pt-based
catalyst for efficient methanol oxidation W. Zhan & L.
Ma & M. Gan
https://ebookmass.com/product/in-situ-growth-of-cop-wrapped-by-
carbon-nanoarray-like-architecture-onto-nitrogen-doped-ti3c2-pt-
based-catalyst-for-efficient-methanol-oxidation-w-zhan-l-ma-m-
gan/

Emerging Applications of Carbon Nanotubes in Drug and

Gene Delivery Prashant Kesharwani

https://ebookmass.com/product/emerging-applications-of-carbon-
nanotubes-in-drug-and-gene-delivery-prashant-kesharwani/

Magnetism and Spintronics in Carbon and Carbon

Nanostructured Materials Sekhar Chandra Ray

https://ebookmass.com/product/magnetism-and-spintronics-in-
carbon-and-carbon-nanostructured-materials-sekhar-chandra-ray/

Winterberries-like 3D network of N-doped porous carbon

anchoring on N-doped carbon nanotubes for highly
efficient platinum-based catalyst in methanol
electrooxidation Tong Wang
https://ebookmass.com/product/winterberries-like-3d-network-of-n-
doped-porous-carbon-anchoring-on-n-doped-carbon-nanotubes-for-
highly-efficient-platinum-based-catalyst-in-methanol-
Industrial Applications of Carbon Nanotubes 1st Edition
Peng Huisheng (Ed.)

https://ebookmass.com/product/industrial-applications-of-carbon-
nanotubes-1st-edition-peng-huisheng-ed/

X-Ray Fluorescence in Biological Sciences: Principles,

Instrumentation, and Applications Vivek K. Singh

https://ebookmass.com/product/x-ray-fluorescence-in-biological-
sciences-principles-instrumentation-and-applications-vivek-k-
singh/

Handbook of Mineral Spectroscopy: X-Ray Photoelectron

Spectra: Volume 1: X-ray Photoelectron Spectra 1st
Edition J. Theo Kloprogge

https://ebookmass.com/product/handbook-of-mineral-spectroscopy-x-
ray-photoelectron-spectra-volume-1-x-ray-photoelectron-
spectra-1st-edition-j-theo-kloprogge/

Addressing the carbon footprint, healthfulness, and

costs of self-selected diets in the USA: a population-
based cross-sectional study Amelia Willits-Smith

https://ebookmass.com/product/addressing-the-carbon-footprint-
healthfulness-and-costs-of-self-selected-diets-in-the-usa-a-
population-based-cross-sectional-study-amelia-willits-smith/

Innovations in Graphene-Based Polymer Composites Sanjay

Mavinkere Rangappa

https://ebookmass.com/product/innovations-in-graphene-based-
polymer-composites-sanjay-mavinkere-rangappa/
 Composites Science and Technology 167 (2018) 148–154

Contents lists available at ScienceDirect

Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Structure of the in situ produced polyethylene based composites modified T

with multi-walled carbon nanotubes: In situ synchrotron X-ray diffraction
and differential scanning calorimetry study
Mariya A. Kazakovaa,b,∗, Alexander G. Selyutina, Nina V. Semikolenovaa, Arcady V. Ishchenkoa,b,
Sergey I. Moseenkova, Mikhail A. Matskoa, Vladimir A. Zakharova, Vladimir L. Kuznetsova,b
a
Boreskov Institute of Catalysis, SB RAS, Lavrentieva 5, Novosibirsk, 630090, Russia
b
Novosibirsk State University, Pirogova 2, Novosibirsk, 630090, Russia

A R T I C LE I N FO A B S T R A C T

Keywords: Polyethylene based composites modified with multi-walled carbon nanotubes (MWCNTs) were produced via in
Multi-walled carbon nanotubes situ polymerization of ethylene with the Ti-Ziegler–Natta catalyst preliminarily immobilized on MWCNTs. The
Polyethylene composites composite structure was characterized with transmission and scanning electron microscopy, differential scan-
In situ polymerization ning calorimetry (DSC) and in situ synchrotron X-ray Diffraction (in situ XRD). For the first time the Ti-containing
Polymer crystallization
catalyst species of the size 2–3 nm were observed on the MWСNTs surface stabilized in the polymer matrix. A
In situ synchrotron X-ray diffraction
comparative study of the melting-crystallization cycles of neat polyethylene (PE) and MWCNT-PE composites
with in situ XRD and DSC provide information on the nucleation of PE crystals. For the first time, the in situ XRD
technique was used for estimation of the coherent scattering region of PE blocks during the melting-crystal-
lization cycles. These experiments and molecular dynamic modeling showed that MWCNTs act as the template
for the PE chain orientation and as the nucleating agent for PE crystallization. However, the nucleation of PE
crystals in composites occurs on the nanotube surface and also within the space between nanotubes. Thus, the
relative volume of PE nucleated on nanotubes depends on their content in the composite and can be significant
only for the composites with high nanotube loading.

1. Introduction properties of polymer-CNT composites. The common methods for the

The outstanding mechanical, electrical and thermal properties of
carbon nanotubes (CNTs) have made them promising materials for a
wide range of applications [1–10]. Generally, most of CNTs are used as
fillers of polymer composites which have the improved mechanical
properties [11–14]. At the same time, CNT incorporation in polymers
provides not only a reinforcement but also an enhancement of other
physical and chemical properties, such as electrical and thermal con-
ductivity, thermal, fire and corrosion resistance [15–23]. The compo-
site properties are determined by the type of CNTs distribution in the
polymer matrix, which in turn is determined by the nature of the na-
notube-polymer interface and the method of CNT incorporation in the
polymer matrix. The interface strength and the wetting ability of na-
notubes with polymer matrices can be varied via functionalization of
the CNT surface [18,24]. The formation of strong interfaces promotes a
better distribution of CNTs in polymer matrices, while the method of
CNT incorporation into polymer is another factor affecting the
preparation of CNT-polymer composites include mechanical mixing
with extrusion, solution mixing, melt blending, coagulation precipita-
tion technique and in situ polymerization [14,25–28].
Previously [25,26], we performed a comparative study of the in-
fluence exerted by the uniformity of the multi-walled carbon nanotubes
(MWCNTs) distribution on the electrophysical properties of MWCNT-PE
composite materials prepared by mechanical mixing in a polymer melt,
coagulation precipitation, and in situ polymerization of ethylene using
Ziegler-Natta catalyst supported on MWCNTs. It was shown that in situ
polymerization yields composite materials with a more uniform dis-
tribution of MWCNTs in the polyethylene (PE) matrix, compared to the
other methods. Investigation of the electrophysical properties of com-
posite materials has shown that uniform distribution of MWCNTs in
polyethylene ensures high values of conductivity, correlating with high
values of the complex dielectric permittivity. At the same time, CNTs
have been reported to act as the nucleating agent for polymer crystal-
lization as well as the template for polymer chain orientation

∗
Corresponding author. Boreskov Institute of Catalysis, SB RAS, Lavrentieva 5, Novosibirsk, 630090, Russia.
E-mail address: mas@catalysis.ru (M.A. Kazakova).

https://doi.org/10.1016/j.compscitech.2018.07.046
Received 13 May 2018; Received in revised form 28 July 2018; Accepted 31 July 2018
Available online 01 August 2018
0266-3538/ © 2018 Elsevier Ltd. All rights reserved.
M.A. Kazakova et al.
[23,29,30].
In the present work, the in situ polymerization technique has been
applied for the preparation of MWCNT/polyethylene composites with
various loadings and morphological structural properties of MWCNTs.
Special attention has been paid to the in situ XRD study on the forma-
tion of structured polyethylene blocks in the melting-crystallization
process. For the first time the in situ synchrotron XRD technique was
used for estimation of the coherent scattering region of PE blocks
during the melting-crystallization cycles. This allowed us to identify the
most important structural features of MWCNT-PE composites that are
related with nucleation and crystallization of PE blocks promoted by
the nanotube surface.
2. Material and methods
Synthesis and post-treatment of MWCNTs. MWCNT samples were
prepared by catalytic gas-phase decomposition of ethylene on the sur-
face of Fe–Co catalyst at 680°С. The MWCNT preparation is described in
more detail in Refs. [31–34]. The characteristics of the prepared
MWCNTs were as follows: the mean diameter 9.4 nm (transmission
electron microscopy data) and the specific surface area 265 m2 g−1
(BET data (SORBI-M instrument, ZAO Meta, Russia). Traces of the
catalyst were removed from the MWCNT samples by boiling in 15%
HCl, followed by washing with distilled water to a neutral pH value.
The MWCNT surfaces were functionalized by boiling for 2 h in con-
centrated nitric acid (ultrapure grade, Reakhim) via grafting of car-
boxyl groups (Fig. 1 A). After the oxidative treatment, the MWCNT
sample was washed with distilled water to a neutral pH value. The
oxidized MWCNT samples are denoted as MWCNT-Ox. Titrimetric
analysis of acidic oxygen-containing groups on the MWCNT surface was
performed using a reverse acid–base titration technique described by
Boehm. Such oxidation conditions provide the formation of 2.4 car-
boxyl groups per 1 nm−2 of the MWCNT surface. According to the TEM
data, the overall morphology of the MWCNT does not practically
change after oxidation treatment. According to the HRTEM, the oxi-
dation of MWCNT leads to a decrease in the amount of amorphous
carbon on the surface of the MWCNT [35]. Moreover, after such oxi-
dative treatment the specific surface area of the MWCNT change within
experimental error ( ± 5%) and was 260 m2/g for MWCNT-Ox.
Deaggregation of MWCNT-Ox, which was aimed to attain more a
uniform distribution in the polyethylene matrix was, performed with an
AGO-2 planetary mill developed at the Institute of Solid State
Chemistry and Mechanochemistry, Siberian Branch of the Russian
Academy of Sciences. The mean length of the milled nanotubes was
about 350 nm (the length varied in the range of 100–3000 nm and was
determined from TEM images of the nanotubes deposited on a Cu grid
from the suspensions in dimethylformamide (Fig. 1B and C) [36]). The
milled MWCNT samples are denoted as MWCNT-M.
Preparation of catalytic systems and synthesis of MWCNT–PE
composite materials by in situ polymerization technique. All ma-
nipulations were carried out under argon atmosphere using standard
Fig. 1. TEM images of oxidized (A) and oxidized-milling (B) MWCNTs. (C) the length distributions of MWCNT-Ox after milling.
149
Composites Science and Technology 167 (2018) 148–154
Schlenk techniques. A MWCNT sample (1–2 g) was placed in a three-
necked glass reactor and dried in a vacuum at 250°С for 4 h. Then, it
was cooled to room temperature and the reactor was filled with argon.
After that, 50–100 mL of heptane was added to the MWCNT samples. A
solution of TIBA in heptane (0.8 mmol/g of MWCNTs) was then added;
the mixture was stirred at room temperature for 1 h and allowed to
settle for 12 h. The liquid phase was decanted and the precipitate was
washed with two portions (50 mL) of pure heptane. The washed sample
of MWCNT/TIBA was supplemented with, 50 mL of heptane, and a
solution of TiCl4 in heptane (0.35 mmol of Ti per gram of MWCNT) was
added under vigorous stirring. The mixture was stirred at room tem-
perature for 30 min, after which the precipitate was allowed to settle
and washed with two portions (50 mL) of pure heptane. Then, 230 mL
of heptane was added, and the catalyst was dispersed by ultrasonic
treatment using an ultrasonic bath Sapfir, 1.3 L. Thus prepared catalyst
suspension was charged into a 1 L steel polymerization reactor pre-
liminarily dried by evacuation at 80 °C and filled with argon. The,
aluminum trialkyl cocatalyst (TIBA or TEA) was added (1.1 mmol), the
mixture was heated to the desired temperature, and ethylene was fed.
During the reaction, the stirring speed, temperature and ethylene
pressure were maintained constant through an automatic computer-
controlled system for the ethylene feed, which recorded the ethylene
consumption. The reaction was performed until the required amount of
the polymer, ensuring the required concentration of MWCNT in the
polymer, was obtained. The samples of MWCNT-PE composite mate-
rials containing 10, 19, 24, 29, and 30 wt% of MWCNTs were prepared.
The polymerization conditions for each experiment are listed in
Table 1. The resulting product was separated, washed with heptane and
ethanol, and dried to the constant weight. Composite films were pre-
pared by pressing of the obtained powder using a hand hot press be-
tween two polished steel plates covered with Teflon® film and copper
frame with a thickness of 0.5 mm as a spacer.
2.1. Characterization of MWCNT–PE composite materials
Transmission electron microscopy (TEM) was carried out using a
JEOL JEM-2010 microscope operating at 200 kV accelerating voltage
and allowing a resolution of 1.4 Å. Energy dispersive X-ray spectro-
scopy (EDS) was undertaken using an EDAX Phoenix system. For TEM
characterization of composite structure, the sample's powder was
placed onto TEM sample support mesh with an amorphous carbon
layer. The size distributions were estimated from a statistical count of
the nanotubes from several frames taken on different parts of the
samples.
Scanning electron microscopy (SEM) was carried out using
JSM6460LV JEOL microscope with acceleration voltage of 25 kV. For
SEM characterization of polymer, composite films were cut into plates
with the size of ca. 8 × 3 × 0.5 mm3, which were glued to the copper
stand with breaks upwards using silver glue. In order to avoid surface
changes during SEM investigations.
Differential scanning calorimetry (DSC) measurements were
M.A. Kazakova et al.
Table 1
The amount of adsorbed TIBA on the surface of different type MWCNTs.
Samples The amount of adsorbed TIBA
MWCNT-ini 0.09 wt % (0.04 mmol Al/g MWCNT)
MWCNT-Ox 0.7 wt % (0.27 mmol Al/g MWCNT)
MWCNT-Ox-M 0.87 wt % (0.34 mmol Al/g MWCNT)
performed using a DSC 204 F1 instrument (Netzsch, Germany) in ac-
cordance with ASTM D3418-82 and ASTM D3417-83 procedures in an
argon atmosphere (flow rate 30 mL min−1) in closed 25-μL aluminum
crucibles. The device was calibrated in accordance with [37,38]. The
calibration was made using indium (99.999%, Aldrich) and zinc (98+
%, Aldrich) as reference samples. The measurement was performed in
the melting–crystallization–melting mode over the temperature range
of 25–180°С at a rate of 10 deg min−1. The melting point Тm and en-
thalpy of melting ΔНm were determined in the second melting run. The
quantity ΔНm was calculated taking into account the MWCNT content
of the sample. The degree of crystallinity Х was calculated using the
equation
X= (ΔHm /290) × 100%,
where ΔНm is the enthalpy of melting of the sample (J g−1), and 290 is
the enthalpy of melting of ideal polyethylene with 100% degree of
crystallinity.
In situ X-ray diffraction (in situ XRD) measurements and de-
termination of the temperature dependence of substructural char-
acteristics of the material's particles after sample annealing were per-
formed on the VEPP 3 Precision Diffractometry station at the Siberian
Center of Synchrotron and Terahertz Radiation. The sample was placed
in an XRK 900 X-ray reactor chamber (Anton Paar, Austria). Heating
was performed in an inert atmosphere from room temperature to 150 °C
at a speed of 10 °C/min, and then the sample was cooled under the same
conditions. Simultaneously, X-ray patterns were recorded on an OD-3M
350 position sensitive detector in the range of 2θ ∼15°–45° with a
discontinuity of ∼0.01° (the operating wavelength 0.1731 nm). Thus,
reflections PE (110) and PE (200) were in the recording range. The
exposure time was 1 min/frame. The X-ray patterns were processed by
measuring the widths of reflections at half-maximum with approxima-
tion of the reflection profile by a pseudo-Voigt function.
2.2. Model and simulation method molecular dynamics simulations of
MWCNT–PE interactions
The molecular modeling software package GROMACS [39–41],
version 4.6.6 was employed to carry out MD simulations using the
OPLS-AA force field [42] in the isothermal–isobaric ensemble (NPT
ensemble). For the NPT ensemble, the number of NPT molecules, the
pressure and temperature of the system are kept constant. The systems
were first stabilized by an energy minimization using 5000 steps of the
steepest descent energy minimization. Further, the MD simulation was
done for 20 ns. All simulations were computed at 300 K and 1 atm, with
a time step of 0.002 ps, and coordinates were stored every 5000 steps,
or 10 ps. Both the temperature and pressure were controlled using the
Berendsen method. For initial equilibration, long-range interactions
were treated with a Coulombic and van der Waals cutoff distance of
1.4 nm to decrease the simulation time. Analyses were performed by
using facilities within the GROMACS package and Visual Molecular
Dynamics (VMD).
3. Results
3.1. Catalyst deposition and polymerization of ethylene
Samples of the initial and oxidized MWCNTs have different
150
Composites Science and Technology 167 (2018) 148–154
Fig. 2. The scheme of immobilization of the catalyst complex on the MWCNT
surface followed by PE polymerization.
functional surface composition. Thus the surface of oxidized MWCNT-
Ox has a large amount of oxygen-containing groups (2.4 carboxyl
groups per 1 nm−2 of the MWCNT surface), and therefore the stability
of their suspensions in heptane differs significantly. Initial MWCNTs
were dispersed carefully in heptane under sonication (the prepared
suspensions with the MWCNT concentration of 20 mg/mL have high
viscosity). Fig. 2 displays the scheme of immobilization of the catalyst
for ethylene polymerization on the surface of MWСNTs.
The amount of the surface centers able to interact with aluminum
trialkyl compound on initial, oxidized and oxidized-milled MWCNTs
was determined by adsorption of the TIBA excess with further careful
washing of the sample. Data on the content of aluminum, determined
by inductively coupled plasma atomic emission spectroscopy, are listed
in Table 1.
We have found that the nature of MWСNTs exerts a pronounced
effect on the amount of adsorbed TIBA used for preparation of the
catalytic system MWСNT-TIBA/TiCl4. The analysis showed that the
oxidation leads to the formation of a large amount of centers that can
react with TIBA on the surface of MWСNTs. Mechanical milling of
oxidized MWCNTs also leads to an additional increase in the adsorption
capacity of TIBA. The amount of adsorbed TIBA correlates with the
surface concentration of carboxylic groups produced via the oxidation
treatment of MWCNTs. The catalytic systems MWCNT-TIBA/TiCl4 were
prepared using different types of MWCNTs and applied for ethylene
polymerization. Table 2 shows the typical conditions for preparing
MWCNT–PE composites by in situ polymerization technique. The sam-
ples of MWCNT-PE composite materials containing 10, 19, 24, 29, and
30 wt% of MWCNTs were produced.
3.2. MWCNT-PE composite characterization
3.2.1. SEM and TEM study of MWCNT-PE composites
Structure and morphology of the prepared MWCNT-PE composites
were studied using TEM and SEM. The SEM analysis of MWCNT-PE
composites was performed to investigate the internal structure of the
materials. The corresponding micrographs of the typical fractures of
MWCNT-PE composites are displayed on Fig. 3.
The distribution of the active catalyst component along the surface
of MWСNTs and uniformity of MWСNTs distribution in the volume of
the polymer matrix were determined by TEM (Fig. 4). The high re-
solution electron micrographs show the 2–3 nm dispersed catalyst
particles (Fig. 4 B) that are distributed quite uniformly along the surface
of the nanotubes. According to EDX analysis data, it was shown that the
polymerization catalyst particles fixed on the MWCNT surface contain
Ti, Cl and Al elements. These data are in a good agreement with our
earlier results obtained by studying the PE morphology that was formed
M.A. Kazakova et al. Composites Science and Technology 167 (2018) 148–154

Table 2
Conditions for preparing MWCNT–PE composites by in situ polymerization technique.
Sample Polymerization conditions Total yield of PE + MWCNTs, g Sample composition, %

MWCNT type and weight, g PC2H4, atm PH2, atm T, °C τ, min PE MWCNTs

1 – 2 – 40 5 8,9 100 –
2 MWCNT initial, 1g 5 – 40 30 3,3 70 30
3 MWCNT-Ox, 2g 3 – 40 21 10.5 81 19
4 MWCNT-Ox, 2g 3 – 40 60 7.0 71 29
5 MWCNT-Ox-M, 1g 4 4 70 33 10.3 90.3 9.7
6 MWCNT-Ox-M, 1g 4 4 70 14 4.4 75.9 24.1
7 MWCNT-Ox-M, 1g 4 4 70 8 4.7 70.3 29.7

at the surfaces of catalyst fillers prepared by TiCl4 anchoring on alu-
minosilicate minerals [43]. As it is evidenced by the formation of
polymer films on the surface of the tubes without a clearly defined
droplet, MWCNTs are uniformly covered by PE molecules (contact
angles cannot be registered, this corresponds to a high work of adhesion
of the polymer to the nanotube surface). The interaction of carbon
nanotubes with polyethylene molecules results in a surface wetting
with polymer, which depends strongly on both the surface composition
of CNTs and the surface properties of the polymer.
3.2.2. In situ XRD and DSC study of MWCNT-PE composites
The structure of all the obtained composites and neat polyethylene
was investigated using in situ XRD on synchrotron radiation. To this
end, the samples were heated in an inert gas to a temperature above the
melting point of PE and then cooled directly in the X-ray reactor
chambers. Fig. 5 shows the typical time resolved XRD patterns of
MWCNT-PE composites during their melting–crystallization cycle.
These data allow getting accurate information on the melting and
crystallization temperatures of PE crystal blocks within the composites
as well as the mean size and defectiveness of PE blocks.
It should be mentioned that the lattice parameter of PE crystals
estimated from the position of the most intensive reflections (110 and
200) did not change after MWCNT incorporation into the composite.
This corresponds to the absence of insertion of nanotube fragments
directly into the polymer crystals. The Scherrer equation was used to
calculate of the size of coherent scattering region (CSR), which corre-
sponds to the mean size of the ordered (crystalline) domains of PE. The
CSR values calculated using the main intensive reflects of PE (110 and
200) were the same for each sample. Fig. 6 summarizes data on the
temperature dependence of CSR of PE crystals during the melting-
crystallization cycles for two sets of composites. The Tcryst values esti-
mated from XRD data are listed in Table 3. Note that Tcryst corresponds
to the temperature of appearance of weak PE reflections (110 and 200),
which were not used for the calculations of CSR due to the low signal-
noise ratio (Fig. 6).
According to the DSC data (Table 3), the introduction of different
type MWCNTs into the polyethylene matrix decreases the melting point
of the polymer by 3–5 °C and the degree of crystallinity by 10–15% in
comparison with neat polyethylene. On the other hand, the melting
point and degree of crystallinity remain high, and the shapes of the
melting and crystallization peaks in the DSC curves are similar to those
of the peaks of neat polyethylene. This fact indicates that the in-
troduction of MWCNTs into polyethylene does not lead to a significant
disordering of its crystal structure. So, we can suppose the existence of
extensive fragments of crystalline polyethylene. This observation cor-
relates with XRD data (the coincidence of the positions of (110) and
(200) reflections with the literature data). DSC data show that Tcryst. for
MWCNT-PE composites is the same or higher than that for neat
polymer. At the same time in situ XRD technique (due its higher sen-
sitivity) registered PE nanocrystals formation at higher temperature.
3.2.3. Molecular dynamics simulations of the formation of MWCNT-PE
composites
To qualitatively assess the formation of MWCNT-PE composites
during the synthesis, the interaction of MWCNTs and PE was simulated
using the molecular dynamics package Gromacs in the OPLS-AA force
field. The first (Fig. 7) image shows the simulated perpendicular ar-
rangement of polyethylene molecules around the tube, which corre-
sponds to the assumed primary direction of growth during the poly-
ethylene synthesis. The initial system consisted of 126 polyethylene
molecules, and each molecule had 180 carbon atoms. The total simu-
lation time was 1500 ps. Eventually, structuring of polyethylene mo-
lecules around the nanotube was observed. Thus, the presence of
MWCNTs provides the appearance of the local preferred direction of
polyethylene growth and the formation of polymer lamellae oriented
along the nanotube axis. From the presented data, it is evident that
MWCNTs contributes to the formation of extended crystal polymer due
to wetting of nanotube by the polymer molecules.
4. Discussion
According to in situ XRD analysis, the CSRs of neat PE (∼150 nm for
110 and 200 reflections), which was produced without nanotube ad-
ditives, were smaller than those of MWCNT-PE composites (∼210 nm,

Fig. 3. Typical SEM images of the MWCNT-PE composite film breaks obtained after cracking at the liquid nitrogen temperature. Bright fragments (dots or villi are
attributed to nanotubes).

151
M.A. Kazakova et al. Composites Science and Technology 167 (2018) 148–154

Fig. 4. TEM images of 30% MWCNT-PE composite. A) MWCNTs homogeneously distributed in the PE matrix; B) PE molecules demonstrate high wetting ability of
nanotube surface; one can see also the 2–3 nm dark spots corresponding to the Ti-containing catalyst particles.

Fig. 5. Typical time resolved in situ XRD patterns of

MWCNT-PE composites during their melting-crystal-
lization cycle. The insert shows variation of the
composite temperature with time. For clarity, only
some of the patterns are presented. It can be seen that
the intensity of PE reflections decreases and dis-
appears near the melting temperature, and then, as
the temperature is lowered, the appearance of PE
reflections is observed again, which corresponds to
crystallization of the polymer. The intensity of the
(002) reflections of MWCNTs was much lower and
much wider than that of PE.

Fig. 6. Temperature dependence of the calculated size of the polyethylene CSR for different composites during the melting-crystallization cycle. A) data for the first
set of the composite produced using MWCNTs without ball milling; B) data for the composite set produced using MWCNTs that were milled and oxidized before
catalyst deposition, and also for neat PE produced without nanotubes. Solid and empty symbols correspond to melting and crystallization, respectively; arrows show
the process direction.

Fig. 6B). A comparison of the CSR changes during PE crystallization in (Fig. 6 A, B). This can be attributed to the fact that the crystallization is
neat polymer and PE-MWCNT composites demonstrates that in the case initiated and initially proceeds on the nanotube surface, and then
of neat PE the size of the polymer crystallites increases during crys- crystallites begin to form in the nanotube free parts of the polymer
tallization, while the PE crystallite size decreases for all the composites volume. Due to the limited volume of the free polymer in the

152
M.A. Kazakova et al.
Table 3
DSC and in situ XRD data of MWCNT-PE composites.
Samples MWCNT-PE composites DSC data Tmelting,°Ca
1 Neat PE 138
2 30% MWCNT-initial/PE 132
3 29% MWCNT-Ox/PE 133
4 19% MWCNT-Ox/PE 135
5 30% MWCNT-Ox-M/PE 136
6 24% MWCNT-Ox-M/PE 138
7 10% MWCNT-Ox-M/PE 139
a
Tmelting corresponds to the maximum of the DSC crystallization curve recorded with a heating rate of 10 °C/min.
b
Tcryst estimated from XRD data corresponds to the temperature of appearance of PE reflections 110 and 200.
Fig. 7. The simulation of the interactions of PE molecules with the surface of MWCNTs.
composites, free polymer crystals of a smaller size are formed. This
leads to a decrease in the relative fraction of the crystallites bound to
the surface of the nanotubes, and, correspondingly, to a decrease in the
observed average size of the polymer crystallites. In the case of neat PE,
the crystallite sizes increase continuously during the crystallization
process. Thus, the relative volume of PE nucleated on nanotubes de-
pends on their content in composite and it can be significant only for
the composites with high nanotube loading.
The oxidation of MWCNTs before the catalyst deposition results in
the formation of smaller PE crystallites (the melting curves in Fig. 6 A)
as compared to the use of initial MWCNTs. The ball milling of the
oxidized MWCNTs before the catalyst deposition results in the forma-
tion of PE crystallites of the same size (the melting curves in Fig. 6 B).
The use of nanotubes not, milled before the catalyst deposition leads to
the formation of PE crystallites of different size because of the diffusion
limitations of ethylene polymerization within the primary aggregates of
nanotubes.
The crystallization of PE after the melting of the composites results
in the formation of PE crystallites which size depends on the MWCNT
content in composites. Thus, the increase in the nanotube content de-
creases the polymer crystallite size (Fig. 6 A, B).
These facts undoubtedly indicate that nanotubes are involved in the
crystallization of PE molecules which are formed directly on the cata-
lyst species generated on the nanotube surface. In other words, CNTs
serve as the nucleating agent for PE crystallization as well as the tem-
plate for the PE chain orientation. This is consistent with the data of
other researchers obtained for different polymers [22] and with the
results of our modeling of the interaction of PE molecules with the
surface of nanotubes.
The comparison of the nucleation of PE initiated by regular nucle-
ating agents (NAs) [44,45] and that initiated by MWCNTs leads to the
conclusion that they should provide a different type of bulk organiza-
tion of the forming polymer crystals during the crystallization following
the nucleation. The nucleation caused by commercial NAs usually
proceeds via the formation of lamellae nucleation centers with their
subsequent transformation into spherulites, which are spherically
153
Composites Science and Technology 167 (2018) 148–154
DSC data Crystallinity, X% DSC data XRD data
Tcryst., °C Tcryst., °Cb
58 113 130
57 115 126
44 113 125
46 114 128
59 114 115
62 112 120
65 113 130
shaped clusters of crystallinity that grow radially from each nucleation
center during crystallization. The spherulites continue to grow until
they reach on the adjacent the spherulites and create a spacefilling
polycrystalline matrix. In the case of PE nucleation on the nanotube
surface lamellae are oriented along the nanotube surface and crystallize
into the PE blocks covering the nanotube.
TEM images of MWCNT-PE composites produced at the early stages
of polymerization do demonstrate the formation of the polymer layers
covering nanotubes. The molecular modeling also supports the or-
ientation of PE lamellae along the nanotube surface. Nevertheless, in
the case of MWCNT-PE composites, the nucleation and crystallization of
PE crystals within the space between nanotubes is also possible during
crystallization stage. The ratio of polymer blocks surrounding a nano-
tube and crystallized in the volume between nanotubes depends on the
concentration of MWCNTs in the composite.
5. Conclusions
The effect of MWCNTs pre-treatment conditions, such as oxidation
and milling, on the formation of MWCNT-PE composites by in situ
polymerization technique has been investigated by in situ XRD, DSC,
SEM and HRTEM. The controlled oxidation and milling treatment of
MWCNTs increases the adsorbing ability of the TIBA-TiCl4 poly-
merization catalyst system with the increased activity. It provides a
homogeneous distribution of the catalyst particles along the nanotubes
and finally a homogeneous coverage of the nanotube surface with PE
molecules. For the first time, we have observed the Ti-containing cat-
alyst species of the size 2–3 nm on the MWСNTs surface stabilized in the
polymer matrix. It was found that CNTs serve as the nucleating agent
for PE crystallization as well as the template for the PE chain orienta-
tion. The crystallization process is initiated and initially proceeds on the
nanotube surface, and then crystallites begin to form in those parts of
the polymer volume that do not contact with nanotubes. Due to the
limited volume of the free polymer in the composites, free polymer
crystals of a smaller size are formed. As revealed by in situ synchrotron
XRD, the oxidation of MWCNTs before the catalyst deposition results in
M.A. Kazakova et al.
the formation of PE crystallites of a smaller size compared with the
initial MWCNTs. The ball milling of the oxidized MWCNTs before the
catalyst deposition results in the formation of PE crystallites of the same
size. The crystallization of PE after the melting of composites results in
the formation of PE crystallites which size depends on the MWCNT
content in the composites. Thus, the increase in the nanotube content
decreases the polymer crystallite size.
In conclusion, we have shown that the use of the in situ poly-
merization technique opens the possibility for the production of
MWCNT-PE composites with a homogeneous distribution of MWCNTs.
MWCNT-PE composites with a high concentration of homogeneously
distributed nanotubes are promising as the polymer carbon nanotubes
conductive masterbatches.
Acknowledgements
This work (study and modeling of composites) was supported by the
Russian Science Foundation (grant 17-73-20293), composites were
produced with support of the Federal Agency of Scientific
Organizations Project.
References
[1] M.F.L. De Volder, S.H. Tawfick, R.H. Baughman, A.J. Hart, Carbon nanotubes:
present and future commercial applications, Science 339 (6119) (2013) 535.
[2] M.S. Dresselhaus, Carbon Nanotubes: Synthesis, Structure, Properties, and
Applications, Springer-Verlag, 2000.
[3] E. Beyou, S. Akbar, P. Chaumont, P. Cassagnau, Polymer nanocomposites con-
taining functionalised multiwalled carbon NanoTubes: a particular attention to
polyolefin based materials, in: S. Suzuki (Ed.), Syntheses and Applications of
Carbon Nanotubes and Their Composites, InTech, Rijeka, 2013, p. 548 Ch. 05.
[4] P. Verma, P. Saini, R.S. Malik, V. Choudhary, Excellent electromagnetic interference
shielding and mechanical properties of high loading carbon-nanotubes/polymer
composites designed using melt recirculation equipped twin-screw extruder, Carbon
89 (2015) 308–317.
[5] Y. Wei, X. Lin, K. Jiang, P. Liu, Q. Li, S. Fan, Thermoacoustic chips with carbon
nanotube thin yarn arrays, Nano Lett. 13 (10) (2013) 4795–4801.
[6] A.S. Andreev, М.A. Kazakova, A.V. Ishchenko, A.G. Selyutin, O.B. Lapina,
V.L. Kuznetsov, J.-B. d'Espinose de Lacaillerie, Magnetic and dielectric properties of
carbon nanotubes with embedded cobalt nanoparticles, Carbon 114 (2017) 39–49.
[7] K. Elumeeva, M.A. Kazakova, D.M. Morales, D. Medina, A. Selyutin, G. Golubtsov,
Y. Ivanov, V. Kuznetzov, A. Chuvilin, H. Antoni, M. Muhler, W. Schuhmann,
J. Masa, Bifunctional oxygen reduction/oxygen evolution activity of mixed Fe/Co
oxide nanoparticles with variable Fe/Co ratios supported on multiwalled carbon
nanotubes, ChemSusChem 11 (7) (2018) 1204–1214.
[8] V.L. Kuznetsov, V.I. Suslyaev, I.O. Dorofeev, M.A. Kazakova, S.I. Moseenkov,
T.E. Smirnova, D.V. Krasnikov, Investigation of electromagnetic properties of
MWCNT aerogels produced via catalytic ethylene decomposition, Phys. Status
Solidi B 252 (11) (2015) 2519–2523.
[9] D.Y. Murzin, E.V. Murzina, A. Aho, M.A. Kazakova, A.G. Selyutin, D. Kubicka,
V.L. Kuznetsov, I.L. Simakova, Aldose to ketose interconversion: galactose and
arabinose isomerization over heterogeneous catalysts, Catal. Sci. Technol. 7 (22)
(2017) 5321–5331.
[10] G. Lalwani, A.T. Kwaczala, S. Kanakia, S.C. Patel, S. Judex, B. Sitharaman,
Fabrication and characterization of three-dimensional macroscopic all-carbon
scaffolds, Carbon 53 (2013) 90–100.
[11] E.T. Thostenson, Z. Ren, T.-W. Chou, Advances in the science and technology of
carbon nanotubes and their composites: a review, Compos. Sci. Technol. 61 (13)
(2001) 1899–1912.
[12] J.N. Coleman, U. Khan, W.J. Blau, Y.K. Gun’ko, Small but strong: a review of the
mechanical properties of carbon nanotube–polymer composites, Carbon 44 (9)
(2006) 1624–1652.
[13] B. Arash, Q. Wang, V.K. Varadan, Mechanical properties of carbon nanotube/
polymer composites, Sci. Rep. 4 (2014) 6479.
[14] Z. Spitalsky, D. Tasis, K. Papagelis, C. Galiotis, Carbon nanotube–polymer compo-
sites: Chemistry, processing, mechanical and electrical properties, Prog. Polym. Sci.
35 (3) (2010) 357–401.
[15] X. Wang, J. Sparkman, J. Gou, Electrical actuation and shape memory behavior of
polyurethane composites incorporated with printed carbon nanotube layers,
Compos. Sci. Technol. 141 (2017) 8–15.
[16] W. Yang, W. Zou, Z. Du, H. Li, C. Zhang, Enhanced conductive polymer nano-
composite by foam structure and polyelectrolyte encapsulated on carbon nano-
tubes, Compos. Sci. Technol. 123 (2016) 106–114.
[17] W. Yu, J. Fu, L. Chen, P. Zong, J. Yin, D. Shang, Q. Lu, H. Chen, L. Shi, Enhanced
thermal conductive property of epoxy composites by low mass fraction of organi-
c–inorganic multilayer covalently grafted carbon nanotubes, Compos. Sci. Technol.
125 (2016) 90–99.
[18] R. Gulotty, M. Castellino, P. Jagdale, A. Tagliaferro, A.A. Balandin, Effects of
functionalization on thermal properties of single-wall and multi-wall carbon
154
Composites Science and Technology 167 (2018) 148–154
nanotube–polymer nanocomposites, ACS Nano 7 (6) (2013) 5114–5121.
[19] R. Abishera, R. Velmurugan, K.V.N. Gopal, Reversible plasticity shape memory
effect in carbon nanotubes reinforced epoxy nanocomposites, Compos. Sci. Technol.
137 (2016) 148–158.
[20] Z. Han, A. Fina, Thermal conductivity of carbon nanotubes and their polymer na-
nocomposites: a review, Prog. Polym. Sci. 36 (7) (2011) 914–944.
[21] C.A. Wilkie, A.B. Morgan, Fire Retardancy of Polymeric Materials, CRC Press, Boca
Raton, 2010.
[22] W. Khan, R. Sharma, P. Saini, Carbon nanotube-based polymer composites: synth-
esis, properties and applications, in: M.R. Berber, I.H. Hafez (Eds.), Carbon
Nanotubes - Current Progress of Their Polymer Composites, InTech, Rijeka, 2016, p.
504 Ch. 01.
[23] Y. Liu, S. Kumar, Polymer/carbon nanotube nano composite fibers–a review, ACS
Appl. Mater. Interfaces 6 (9) (2014) 6069–6087.
[24] P.-C. Ma, N.A. Siddiqui, G. Marom, J.-K. Kim, Dispersion and functionalization of
carbon nanotubes for polymer-based nanocomposites: a review, Compos. Appl. Sci.
Manuf. 41 (10) (2010) 1345–1367.
[25] M.A. Kazakova, V.L. Kuznetsov, N.V. Semikolenova, S.I. Moseenkov,
D.V. Krasnikov, M.A. Matsko, A.V. Ishchenko, V.A. Zakharov, A.I. Romanenko,
O.B. Anikeeva, E.N. Tkachev, V.I. Suslyaev, V.A. Zhuravlev, K.V. Dorozkin,
Comparative study of multiwalled carbon nanotube/polyethylene composites pro-
duced via different techniques, Phys. Status Solidi B 251 (12) (2014) 2437–2443.
[26] M.A. Kazakova, N.V. Semikolenova, E.Y. Korovin, S.I. Moseenkov, A.S. Andreev,
A.S. Kachalov, V.L. Kuznetsov, V.I. Suslyaev, M.A. Mats’ko, V.A. Zakharov, In situ
polymerization technique for obtaining composite materials based on polyethylene,
multi-walled carbon nanotubes and cobalt nanoparticles, Russ. J. Appl. Chem. 91
(1) (2018) 127–135.
[27] S.I. Moseenkov, V.D. Krasnikov, V.I. Suslyaev, E.Yu. Korovin, K.V. Dorozhkin,
V.L. Kuznetsov, Influence of carbon nanotube spatial distribution on electro-
magnetic properties of nanotube–polymer composites, Phys. Status Solidi B 255 (1)
(2017) 1700257.
[28] A. Funck, W. Kaminsky, Polypropylene carbon nanotube composites by in situ
polymerization, Compos. Sci. Technol. 67 (5) (2007) 906–915.
[29] R. Haggenmueller, J.E. Fischer, K.I. Winey, Single wall carbon nanotube/poly-
ethylene Nanocomposites: nucleating and templating polyethylene crystallites,
Macromolecules 39 (8) (2006) 2964–2971.
[30] F. Zuo, C. Burger, X. Chen, Y. Mao, B.S. Hsiao, H. Chen, G.R. Marchand, S.-Y. Lai,
D. Chiu, An in situ x-ray structural study of olefin block and random copolymers
under uniaxial deformation, Macromolecules 43 (4) (2010) 1922–1929.
[31] V.L. Kuznetsov, S.N. Bokova-Sirosh, S.I. Moseenkov, A.V. Ishchenko,
D.V. Krasnikov, M.A. Kazakova, A.I. Romanenko, E.N. Tkachev, E.D. Obraztsova,
Raman spectra for characterization of defective CVD multi-walled carbon nano-
tubes, Phys. Status Solidi B 251 (12) (2014) 2444–2450.
[32] S.N. Bokova-Sirosh, V.L. Kuznetsov, A.I. Romanenko, M.A. Kazakova,
D.V. Krasnikov, E.N. Tkachev, Y.I. Yuzyuk, E.D. Obraztsova, Investigation of de-
fectiveness of multiwalled carbon nanotubes produced with Fe–Co catalysts of
different composition, J. Nanophotonics 10 (1) (2016) 012526 (1-10).
[33] A.S. Andreev, D.V. Krasnikov, V.I. Zaikovskii, S.V. Cherepanova, M.A. Kazakova,
O.B. Lapina, V.L. Kuznetsov, J.B. d'Espinose de Lacaillerie, Internal field 59Co NMR
study of cobalt-iron nanoparticles during the activation of CoFe2/CaO catalyst for
carbon nanotube synthesis, J. Catal. 358 (2018) 62–70.
[34] M.A. Kazakova, V.L. Kuznetsov, S.N. Bokova-Sirosh, D.V. Krasnikov,
G.V. Golubtsov, A.I. Romanenko, I.P. Prosvirin, A.V. Ishchenko, A.S. Orekhov,
A.L. Chuvilin, E.D. Obraztsova, Fe–Mo and Co–Mo catalysts with varying compo-
sition for multi-walled carbon nanotube growth, Phys. Status Solidi B 255 (1)
(2018) 1700260.
[35] M.A. Kazakova, A.S. Andreev, A.G. Selyutin, A.V. Ishchenko, A.V. Shuvaev,
V.L. Kuznetsov, O.B. Lapina, J.-B. d'Espinose de Lacaillerie, Co metal nanoparticles
deposition inside or outside multi-walled carbon nanotubes via facile support pre-
treatment, Appl. Surf. Sci. 456 (2018) 657–665.
[36] G.M. Mikheev, V.L. Kuznetsov, K.G. Mikheev, T.N. Mogileva, M.A. Shuvaeva,
S.I. Moseenkov, Laser modification of optical properties of a carbon nanotube
suspension in dimethylformamide, Tech. Phys. Lett. 39 (4) (2013) 337–340.
[37] V.A. Drebushchak, Calibration coefficient of a heat-flow DSC. Part I. Relation to the
Sensitivity of a thermocouple, J. Therm. Anal. Calorim. 76 (3) (2004) 941–947.
[38] V.A. Drebushchak, Calibration coefficient of a heat-flow DSC; Part II. Optimal ca-
libration procedure, J. Therm. Anal. Calorim. 79 (1) (2005) 213–218.
[39] H.J.C. Berendsen, D. van der Spoel, R. van Drunen, GROMACS: a message-passing
parallel molecular dynamics implementation, Comput. Phys. Commun. 91 (1)
(1995) 43–56.
[40] E. Lindahl, B. Hess, D. van der Spoel, GROMACS 3.0: a package for molecular si-
mulation and trajectory analysis, Mol. Model. Annu. 7 (8) (2001) 306–317.
[41] D. Van Der Spoel, E. Lindahl, B. Hess, G. Groenhof, E. Mark Alan, J.C. Berendsen
Herman, GROMACS: fast, flexible, and free, J. Comput. Chem. 26 (16) (2005)
1701–1718.
[42] W.L. Jorgensen, D.S. Maxwell, J. Tirado-Rives, Development and testing of the
OPLS all-atom force field on conformational energetics and properties of organic
liquids, J. Am. Chem. Soc. 118 (45) (1996) 11225–11236.
[43] N.V. Semikolenova, G.A. Nesterov, V.A. Zakharov, G.N. Krjukova, V.P. Ivanov,
G.I. Gol'denberg, The effect of active site composition and support structure in
supported catalysts on the nascent morphology of polyethylene, Makromol. Chem.
189 (8) (1988) 1739–1753.
[44] K.M. Seven, J.M. Cogen, J.F. Gilchrist, Nucleating agents for high‐density poly-
ethylene—a review, Polym. Eng. Sci. 56 (5) (2016) 541–554.
[45] C.M. Zhang, B.-H. Guo, J. Xu, A review on polymer crystallization theories, Crystals
7 (1) (2017).
Another random document with
no related content on Scribd:
radial canals. Carmarina of the Mediterranean and other seas
becomes larger even than Geryonia, from which it differs in the
arrangement of the centripetal canals.

Liriantha appendiculata sometimes occurs on the south coast of

England during September, October, or at other times.

Order VIII. Narcomedusae.

The Narcomedusae differ from the Trachomedusae in having the
margin of the umbrella divided into a number of lobes, and in bearing
the gonads on the sub-umbrellar wall of the gastral cavity instead of
upon the radial canals. The tentacles are situated at some little
distance from the margin of the umbrella at points on the aboral
surface corresponding with the angles between the umbrella lobes.
Between the base of the tentacle and the marginal angle there is a
tract of modified epithelium called the "peronium." The manubrium is
usually short, and the mouth leads into an expanded gastral
chamber which is provided with lobular diverticula reaching as far as
the bases of the tentacles. The marginal sense-organs are in the
form of unprotected statorhabs. Very little is known concerning the
life-history of any of the Narcomedusae. In Cunoctantha octonaria
the peculiar ciliated larva with two tentacles and a very long
proboscis soon develops two more tentacles and creeps into the bell
of the Anthomedusan Turritopsis, where, attached by its tentacles, it
lives a parasitic life. Before being converted into a Medusa it gives
rise by gemmation to a number of similar individuals, all of which
become, in time, Medusae. The parasitic stage is often regarded as
the representative of the hydrosome stage reduced and adapted to
the oceanic habit of the adult.
In Cunina proboscidea, and in some other species, a very
remarkable method of reproduction has been described by
Metschnikoff, called by him "sporogony." In these cases young
sexual cells (male or female) wander from the gonad of the parent
into the mesogloea of the umbrella, where they develop
parthenogenetically into ciliated morulae. These escape by the radial
canals into the gastric cavity, and there form a stolon from which
young Medusae are formed by gemmation. In C. proboscidea these
young Medusae are like the genus Solmaris, but in C. rhododactyla
they have the form of the parent. In some cases the ciliated larvae
leave the parent altogether and become attached to a Geryonia or
some other Medusa, where they form the stolon.

This very interesting method of reproduction cannot be regarded as

a primitive one, and throws no light on the origin of the order. It might
be regarded as a further stage in the degeneration of the hydrosome
stage in its adaptation to a parasitic existence.

The Narcomedusae have a wide geographical distribution. Species

of Aeginopsis occur in the White Sea and Bering Strait, but the
genera are more characteristic of warmer waters. Some species
occur in moderately deep water, and Cunarcha was found in 1675
fathoms off the Canaries, but they are more usually found at or near
the surface of the sea.

Fam. Cunanthidae.—Narcomedusae with large gastral diverticula

corresponding in position with the bases of the tentacles. Cunina and
Cunoctantha, occurring in the Mediterranean and in the Atlantic and
Pacific Oceans, belong to this family. In Cunina the tentacles may be
eight in number, or some multiple of four between eight and twenty-
four. In Cunoctantha the number of tentacles appears to be
constantly eight.

Fam. Peganthidae.—There appear to be no gastral pouches in this

family. The species of Pegantha are found at depths of about 80
fathoms in the Indian and Pacific Oceans.
Fam. Aeginidae.—The large gastral pouches of this family alternate
with the bases of the tentacles. Aegina occurs in the Atlantic and
Pacific Oceans. Aeginopsis.

Fam. Solmaridae.—In this family the gastral pouches are variable,

sometimes corresponding with, sometimes alternating with, the
bases of the tentacles. The circular canal is represented in some
genera by solid cords of endoderm. Solmaris sometimes appears in
the English Channel, but it is probably a wanderer from the warmer
regions of the Atlantic Ocean. It is found in abundance during
November on the west coast of Ireland.

Order IX. Siphonophora.

In this order the naturalist finds collected together a number of very
beautiful, delicate transparent organisms to which the general term
"jelly-fish" may be applied, although their organisation is far more
complicated and difficult to describe than that of any of the Medusae.
In several of the Hydrozoa the phenomenon of dimorphism has
already been noticed. In these cases one set of individuals in a
colony performs functions of stinging and catching food and another
the functions of devouring and digesting it. In many of the
Siphonophora there appears to be a colony of individuals in which
the division of labour is carried to a much further extent than it is in
the dimorphic Hydrozoa referred to above. Not only are there
specialised gastrozooids and dactylozooids, but also gonozooids,
zooids for propelling the colony through the water ("nectocalyces"),
protective zooids ("hydrophyllia"), and in some cases a specialised
zooid for hydrostatic functions; the whole forming a swimming or
floating polymorphic colony. But this conception of the construction
of the Siphonophora is not the only one that has met with support.
By some zoologists the Siphonophoran body is regarded not as a
colony of individuals, but as a single individual in which the various
organs have become multiplied and dislocated.
The multiplication or repetition of organs that are usually single in
each individual is not unknown in other Hydrozoa. In the Medusa of
the Gymnoblast Syncoryne, usually known as Sarsia, for example,
there is sometimes a remarkable proliferation of the manubrium, and
specimens have been found with three or four long manubria
attached by a tubular stalk to the centre of the umbrella. Moreover,
this complex of manubria may become detached from the umbrella
and live for a considerable time an independent existence.[333]

If we regard the manubrium of a Medusa as an organ of the animal's

body, it might be thought obvious that the phenomenon observed in
the Medusae of Syncoryne is a case of a simple repetition of the
parts of an individual; but the power that the group of manubria
possesses of leading an independent existence renders its
interpretation as a group of organs a matter of some inconvenience.
If we can conceive the idea that an organ may become detached
and lead an independent existence, there is no reason why we
should not regard the Medusa itself of Syncoryne as an organ, and
we should be driven to the paradoxical conclusion that, as regards
several genera and families of Hydrozoa, we know nothing at
present of the individuals, but only of their free-swimming organs,
and that in others the individual has degenerated, although one of its
organs remains.

There is, however, no convincing argument to support either the

conception that the Siphonophoran body is a colony of individuals, or
that it is an individual with disjointed organs. These two conceptions
are sometimes called the "Poly-person" and "Poly-organ" theories
respectively. The difficulty is caused by the impossibility of giving any
satisfactory definition in the case of the Hydrozoa of the biological
terms "organ" and "individual." In the higher animals, where the
correlation of parts is far more complex and essential than it is in
Coelenterata, a defined limit to the scope of these terms can be laid
down, but in the lower animals the conception of what is termed an
organ merges into that which is called an individual, and no definite
boundary line between the two exists in Nature. The difficulty is
therefore a permanent one, and, in using the expression "colony" for
the Siphonophoran body, it must be understood that it is used for
convenience' sake rather than because it represents the only correct
conception of the organisation of these remarkable Coelenterates.

Regarding the Siphonophora as polymorphic colonies, then, the

following forms of zooids may be found.

Nectocalyces.—The nectocalyces are in the form of the umbrella of

a medusa attached to the stolon of the colony by the aboral pole.
They are provided with a velum and, usually, four radial canals and a
circular canal. There is no manubrium, and the marginal tentacles
and sense-organs are rudimentary or absent. There may be one or
more nectocalyces in each colony, and their function is, by rhythmic
contractions, to propel the colony through the water (Fig. 142, N).

Gastrozooids.—These are tubular or saccular zooids provided with a

mouth and attached by their aboral extremity to the stolon (Fig. 142,
G). In some cases the aboral region of the zooid is differentiated as
a stomach. It is dilated and bears the digestive cells, the oral
extremity or hypostome being narrower and more transparent. In
some cases the mouth is a simple round aperture at the extremity of
the hypostome, but in others it is dilated to form a trumpet-like lip.

Dactylozooids.—In Velella and Porpita the dactylozooids are similar

in general characters to the tentacles of many Medusae. They are
arranged as a frill round the margin of the colony, and each consists
of a simple tube of ectoderm and endoderm terminating in a
knobbed extremity richly provided with nematocysts.

In many other Siphonophora, however, the dactylozooids are very

long and elaborate filaments, which extend for a great distance from
the colony into the sea. They reach their most elaborate condition in
the Calycophorae.
 Fig. 141.—A small Crustacean (Rhinocalanus) caught by a terminal filament (f.t)
of a battery of Stephanophyes. b, The proximal end of the battery with the
most powerful nematocysts; e, elastic band; S, stalk supporting the battery
on the dactylozooid. (After Chun.)

The dactylozooid in these forms has a hollow axis, and the lumen is
continuous with the cavity of the neighbouring gastrozooid. Arranged
at regular intervals on the axis is a series of tentacles ("tentilla"), and
each of these supports a kidney-shaped swelling, the "cnidosac," or
battery, which is sometimes protected by a hood. Each battery
contains an enormous number of nematocysts. In Stephanophyes,
for example, there are about 1700 nematocysts of four different
kinds in each battery. At the extremity of the battery there is a
delicate terminal filament. The action of the battery in
Stephanophyes is, according to Chun,[334] a very complicated one.
The terminal filament lassos the prey and discharges its somewhat
feeble nematocysts at it (Fig. 141). If this kills it, the dactylozooid
contracts and passes the prey to a gastrozooid. If the animal
continues its struggles, it is drawn up to the distal end of the battery
and receives the discharge of a large number of nematocysts; and if
this also fails to put an end to its life, a membrane covering the
largest and most powerful nematocysts at the proximal end of the
whole battery is ruptured, and a final broadside of stinging threads is
shot at it.
The larger nematocysts of these batteries in the Siphonophora are
among the largest found in Coelenterata, being from 0.5 to 0.1 mm.
in length, and they are frequently capable of inflicting painful stings
on the human skin. The species of Physalia, commonly called
"Portuguese Men-of-War," have perhaps the worst reputation in this
respect, the pain being not only intense but lasting a long time.

Hydrophyllia.—In many Siphonophora a number of short, mouthless,

non-sexual zooids occur, which appear to have no other function
than that of shielding or protecting other and more vital parts of the
colony. They consist of an axis of firm mesogloea, covered by a layer
of flattened ectoderm, and they may be finger-shaped or triangular in
form. In Agalma and Praya an endoderm canal perforates the
mesogloea and terminates in a little mouth at the free extremity. In
Athoria and Rhodophysa the hydrophyllium terminates in a little
nectocalyx.

Pneumatophore.—In all the Siphonophora, with the exception of the

Calycophorae, there is found on one side or at one extremity of the
colony a vesicle or bladder containing a gas,[335] which serves as a
float to support the colony in the water. This bladder or
pneumatophore is probably in all cases a much modified nectocalyx.
It shows great variations in size and structure in the group. It is
sometimes relatively very large, as in Physalia and Velella,
sometimes very small, as in Physophora. It is provided with an apical
pore in some genera (Rhizophysa), or a basal pore in others
(Auronectidae), but it is generally closed. In the many chambered
pneumatophore of the Chondrophoridae there are several pores.

In many forms two distinct parts of the pneumatophore can be

recognised—a distal region lined by chitin,[336] probably
representing the sub-umbrellar cavity of the nectocalyx, and a small
funnel-shaped region lined by an epithelium, the homology of which
is a matter of dispute. It is believed that the gas is secreted by this
epithelium. In the Auronectidae the region with secretory epithelium
is relatively large and of a more complicated histological character. It
is remarkable also that in this family the pore communicates, not with
the chitin-lined region, but directly with the epithelium-lined region.

There is no pneumatophore in the Calycophorae, but in this sub-

order a diverticulum of an endoderm canal secretes a globule of oil
which may serve the same hydrostatic function.

The stolon is the common stem which supports the different zooids
of the colony. In the Calycophorae the stolon is a long, delicate, and
extremely contractile thread attached at one end to a nectocalyx,
and bearing the zooids in discontinuous groups. These groups of
zooids arranged at intervals on the stolon are called the "cormidia."
The stolon is a tube with very thick walls. Its lumen is lined by a
ciliated endoderm with circular muscular processes, and the surface
is covered with an ectoderm, also provided with circular muscular
processes. Between these two layers there is a relatively thick
mesogloea showing on the outer side deep and compound folds and
grooves supporting an elaborate system of longitudinal muscular
fibres. In many Physonectidae the stolon is long and filamentous, but
not so contractile as it is in Calycophorae, but in others it is much
reduced in length and relatively stouter. The reduction in length of
the stolon is accompanied by a complication of structure, the simple
tubular condition being replaced by a spongy complex of tubes
covered by a common sheath of ectoderm. In the Auronectidae the
stolon is represented by a conical or hemispherical spongy mass
bearing the zooids, and in the Rhizophysaliidae and
Chondrophoridae it becomes a disc or ribbon-shaped pad spreading
over the under side of the pneumatophore.

Gonozooids.—The gonozooids are simple tubular processes

attached to the stolon which bear the Medusae or the degenerate
medusiform gonophores. In the Chondrophoridae the gonozooids
possess a mouth, but in most Siphonophora they have neither mouth
nor tentacles. In some cases, such as Anthophysa, the colonies are
bisexual—the male and female gonophores being borne by separate
gonozooids—but in others (e.g. Physalia) the colonies appear to be
unisexual.

As a general rule the gonophores of Siphonophora do not escape

from the parent colony as free-swimming Medusae, but an exception
occurs in Velella, which produces a number of small free-swimming
Medusae formerly described by Gegenbaur under the generic name
Chrysomitra. This Medusa has a velum, a single tentacle, eight to
sixteen radial canals, and it bears the gonads on the short
manubrium. The Medusa of Velella has, in fact, the essential
characters of the Anthomedusae.

Our knowledge of the life-history of the Siphonophora is very

incomplete, but there are indications, from scattered observations,
that in some genera, at least, it may be very complicated.

The fertilised ovum of Velella gives rise to a planula which sinks to

the bottom of the sea, and changes into a remarkable larva known
as the Conaria larva. This larva was discovered by Woltereck[337] at
depths of 600-1000 metres in great numbers. It is very delicate and
transparent, but the endoderm is red (the colour so characteristic of
animals inhabiting deep water), and it may be regarded as
essentially a deep-sea larva. The larva rises to the surface and
changes into the form known as the Ratarula larva, which has a
simple one-chambered pneumatophore containing a gas, and a
rudiment of the sail. In contrast to the Conaria, the Ratarula is blue in
colour. With the development of the zooids on the under side of this
larva (i.e. the side opposite to the pneumatophore), a definite
octoradial symmetry is shown, there being for some time eight
dactylozooids and eight definite folds in the wall of the
pneumatophore. This octoradial symmetry, however, is soon lost as
the number of folds in the pneumatophore and the number of
tentacles increase.
It is probable that in the Siphonophora, as in many other
Coelenterata, the production of sexual cells by an individual is no
sign that its life-history is completed. There may possibly be two or
more phases of life in which sexual maturity is reached.

An example of a complicated life-history is found in the

Calycophoran species Muggiaea kochii. The embryo gives rise to a
form with a single nectocalyx which is like a Monophyes, and this by
the budding of a second nectocalyx produces a form that has a
remarkable resemblance to a Diphyes, but the primary nectocalyx
degenerates and is cast off, while the secondary one assumes the
characters of the single Muggiaea nectocalyx. The stolon of the
Muggiaea produces a series of cormidia, and as the sexual cells of
the cormidia develop, a special nectocalyx is formed at the base of
each one of them, and the group of zooids is detached as an
independent colony, formerly known as Eudoxia eschscholtzii. In a
similar manner the cormidia of Doramasia picta give rise to the
sexual free-swimming monogastric forms, known by the name
Ersaea picta (Fig. 142). In these cases it seems possible that the
production of ripe sexual cells is confined to the Eudoxia and Ersaea
stages respectively, but it is probable that in other species the
cormidia do not break off from the stolon, or may escape only from
the older colonies.

Fig. 142.—Free-swimming Ersaea group of Doramasia picta. B, B, batteries of

nematocysts borne by the tentilla; D, dactylozooid; G, gastrozooid; H,
hydrophyllium; N, nectocalyx; O, oleocyst; f.t, terminal filament of a battery;
t, t, tentilla. The gonozooid is hidden by the gastrozooid. × 10. (After Chun.)
The Siphonophora are essentially free-swimming pelagic organisms.
Some of them (Auronectidae) appear to have become adapted to a
deep-sea habit, others are usually found in intermediate waters, but
the majority occur with the pelagic plankton at or very near the
surface of the open sea. Although the order may be said to be
cosmopolitan in its distribution, the Siphonophora are only found in
great numbers and variety in the sub-tropical and tropical zones. In
the temperate and arctic zones they are relatively rare, but
Galeolaria biloba and Physophora borealis appear to be true
northern forms. The only British species are Muggiaea atlantica and
Cupulita sarsii. Velella spirans occasionally drifts from the Atlantic on
to our western shores, and sometimes great numbers of the
pneumatophores of this species may be found cast up on the beach.
Diphyes sp., Physalia sp., and Physophora borealis are also
occasionally brought to the British shores by the Gulf Stream.

The Calycophorae are usually perfectly colourless and transparent,

with the exception of the oil-globule in the oleocyst, which is yellow
or orange in colour. Many of the other Siphonophora, however, are of
a transparent, deep indigo blue colour, similar to that of many other
components of the plankton.

Most of the Siphonophora, although, strictly speaking, surface

animals, are habitually submerged; the large pneumatophores of
Velella and Physalia, however, project above the surface, and these
animals are therefore frequently drifted by the prevailing wind into
large shoals, or blown ashore. At Mentone, on the Mediterranean,
Velella is sometimes drifted into the harbour in countless numbers.
Agassiz mentions the lines of deep blue Velellas drifted ashore on
the coast of Florida; and a small species of blue Physalia may often
be seen in long lines on the shore of some of the islands of the
Malay Archipelago.

The food of most of the Siphonophora consists of small Crustacea

and other minute organisms, but some of the larger forms are
capable of catching and devouring fish. It is stated by Bigelow[338]
that a big Physalia will capture and devour a full-grown Mackerel.
The manner in which it feeds is described as follows:—"It floats on
the sea, quietly waiting for some heedless individual to bump its
head against one of the tentacles. The fish, on striking, is stung by
the nettle-cells, and fastened probably by them to the tentacle.
Trying to run away the fish pulls on the tentacle. The tension on its
peduncle thus produced acts as a stimulus on apparently some
centre there which causes it to contract. The fish in this way is drawn
up so that it touches the sticky mouths of the squirming siphons [i.e.
gastrozooids]. As soon as the mouths, covered as they are with a
gluey substance and provided with nettle-cells, touch the fish they
stick fast, a few at first, and gradually more. The mouths open, and
their lips are spread out over the fish until they touch, so that by the
time he is dead the fish is enclosed in a tight bag composed of the
lips of a dozen or more siphon mouths. Here the fish is digested. As
it begins to disintegrate partially digested fragments are taken into
the stomachs of the attached siphons (gastrozooids). When they
have become gorged they detach themselves from the remains of
the fish, the process of digestion is completed in the stomachs, and
the nutrient fluid is distributed...."

In consequence of the very unsatisfactory state of our knowledge of

the life-history of the Siphonophora the classification of the order is a
matter of unusual difficulty.

Sub-Order I. Calycophorae.
The character which distinguishes this sub-order is the absence of a
pneumatophore.

The colony usually consists of a long, slender, contractile stolon,

provided at one end with one, two, or several nectocalyces. Upon
the stolon are arranged several groups ("cormidia") of polymorphic
zooids.
The nectocalyces have a well-developed velum, four radial canals,
and a muscular umbrella-wall. A special peculiarity of the nectocalyx
of this sub-order is a diverticulum (oleocyst) from one of the radial
canals, containing a coloured globule of oil. The function of this oil-
globule is probably similar to that of the pneumatophore, and assists
the muscular efforts of the nectocalyces in keeping the colony afloat.
One of the nectocalyces of each colony exhibits on one side a deep
ectodermic fold, which is frequently converted into a pit. At the
bottom of this pit is attached the end of the stolon, the whole of
which with its numerous cormidia can be withdrawn into the shelter
of the pit when danger threatens. The cormidia consist of at least
four kinds of zooids: a gastrozooid with a trumpet-shaped mouth
armed with nematocysts, a long dactylozooid provided with a series
of tentilla, and a rudimentary gonozooid bearing numbers of male or
female medusiform gonophores. These three kinds of zooids are
partially covered and protected by a bent shield-shaped phyllozooid
or hydrophyllium.

Each of the cormidia is unisexual, but the colony as a whole is

usually hermaphrodite, the male and female cormidia regularly
alternating, or the male cormidia being arranged on the
nectocalycine half and the female cormidia on the opposite half of
the stolon.

The families of the Calycophorae are:—

Fam. 1. Monophyidae.—In this family there is a single conical or

mitre-shaped nectocalyx. The cormidia become detached as free-
swimming Eudoxia or Ersaea forms.

Sub-Fam. 1. Sphaeronectinae.—The primary nectocalyx persists

throughout life—Monophyes and Sphaeronectes.

Sub-Fam. 2. Cymbonectinae.—The primary nectocalyx is thrown

off, and is replaced by a secondary and permanent nectocalyx—
Cymbonectes, Muggiaea, and Doramasia.

Fam. 2. Diphyidae.—The primary mitre-shaped nectocalyx is thrown

off and replaced by two secondary rounded, prismatic, or pyramidal,
heteromorphic nectocalyces.

This family contains several sub-families, which are arranged in two

groups: the Diphyidae Oppositae, in which the two secondary bells
are opposite one another, and do not exhibit pronounced ridges; and
the Diphyidae Superpositae, in which one of the two secondary
nectocalyces is situated in front of the other, and each nectocalyx is
provided externally with very definite and often wing-like ridges. In all
the Diphyidae Oppositae the cormidia remain attached, whereas in
most of the Diphyidae Superpositae they become free-swimming, as
in the Monophyidae.

The sub-families of the Diphyidae Oppositae are:—

Sub-Fam. 1. Amphicaryoninae.—One of the two secondary

nectocalyces becomes flattened above to form a shield, and at the
same time its sub-umbrellar cavity is atrophied, and its radial canals
reduced. Mitrophyes, Atlantic Ocean.

Sub-Fam. 2. Prayinae.—The colony exhibits a pair of large, obtuse

nectocalyces, with a relatively small sub-umbrellar cavity. Praya,
Mediterranean and Atlantic.

Sub-Fam. 3. Desmophyinae.—The colony bears a large number of

reserve or tertiary nectocalyces arranged in two rows. Desmophyes,
Indian Ocean.

Sub-Fam. 4. Stephanophyinae.—There are four nectocalyces

arranged in a horizontal plane. Each one of the cormidia bears a
nectocalyx, which is periodically replaced. This sub-family is
constituted for Stephanophyes superba from the Canary Islands. It
attains a length of 25 cm., and is probably the largest and most
beautiful of all the Calycophoridae.[339]

The group Diphyidae Superpositae contains the following:—

Sub-Fam. 1. Galeolarinae.—Galeolaria.

Sub-Fam. 2. Diphyopsinae.—Diphyes.

Sub-Fam. 3. Abylinae.—Abyla.

These sub-families differ from one another in the character and

shape of the nectocalyces and in other characters. They have a
world-wide distribution, Diphyes and Galeolaria extending north into
the Arctic Seas. Diphyes is British.

Fam. 3. Polyphyidae.—The nectocalyces are numerous, and

superposed in two rows. The cormidia remain attached.

The family contains the genera Polyphyes and Hippopodius, both

probably cosmopolitan in warm waters.

Sub-Order II. Physophorae.

In this sub-order the primary nectocalyx gives rise to a definite
pneumatophore. There are four families.

Fam. 1. Physonectidae.—In this, the largest family of the sub-order,

there is a monothalamic pneumatophore supporting a stolon, which
in some forms is of great length, but in others is reduced to a stump
or pad, on which there are usually found several nectocalyces,
hydrophyllia, gastrozooids, gonozooids, and tentilla.
The principal sub-families are:—

Agalminae.—With a long stolon, bearing at the upper end (i.e. the

end next to the pneumatophore) two rows of nectocalyces. The other
zooids are arranged in cormidia on the stolon, each covered by a
hydrophyllium. Dactylozooids with tentilla. Agalma and Cupulita,
Mediterranean Sea.

Apoleminae.—Similar to the above, but without tentilla. Apolemia—

this genus attains a length of two or three metres. Mediterranean
Sea. Dicymba, Indian Ocean.

Physophorinae.—The pneumatophore larger in proportion than it is

in the preceding families. The stolon is short, and bears rows of
nectocalyces at the upper end. The gastrozooids, dactylozooids, and
gonozooids are arranged in verticils on the lower expanded part of
the stolon. Hydrophyllia absent. Physophora, cosmopolitan in the
areas of warm sea water.

Fam. 2. Auronectidae.—The pneumatophore is large. The stolon is

reduced to a spongy mass of tissue on the under side of the
pneumatophore, and this bears numerous cormidia arranged in a
helicoid spiral. Projecting from the base of the pneumatophore there
is a peculiar organ called the "aurophore," provided with an apical
pore. This organ has been described as a specially modified
nectocalyx, but it is probably a specialised development of the
epithelium-lined portion of the pneumatophore of other Physophorae.
The Auronectidae are found only at considerable depths, 300 to
1400 fathoms, and are probably specially adapted to that habitat.
Rhodalia, Stephalia, Atlantic Ocean.

Fam. 3. Rhizophysaliidae.—The pneumatophore is large, or very

large, in this family. The zooids are arranged in horizontal rows on
the under side of the pneumatophore (Physalia), or in a helicoid
spiral on a short stolon (Epibulia). There are no nectocalyces nor
hydrophyllia.

The genus Physalia is the notorious "Portuguese Man-of-War." The

pneumatophore is a large bladder-like vesicle, sometimes attaining a
length of 12 cm. One species described by Haeckel under the
generic name Caravella has a pneumatophore 30 cm. and more in
length, and dactylozooids attaining a length of 20 metres. It is a
curious fact that only the male colonies of Physalia are known, and it
is suggested that the female may have quite a different form.[340]
Epibulia has a much smaller bladder than Physalia. Both genera
have a cosmopolitan distribution at the surface of the warm seas.

Fam. 4. Chondrophoridae.—This family stands quite by itself in the

sub-order Physophorae, and is placed in a separate division of the
sub-order by Chun, who gives it the name Tracheophysa. The
essential distinguishing characters of the family are the large
polythalamic pneumatophore and the single large central
gastrozooid.

The colony is disc-shaped, and has a superficial resemblance to a

Medusa. On the upper side is the flattened pneumatophore, covered
by a fold of tissue continuous with that at the edge of the disc. In
Velella a vertical triangular sail or crest rises from the upper side, but
this is absent in Porpita.

The mouth of the gastrozooid opens into a large digestive cavity, and
between this and the under surface of the pneumatophore there is a
glandular spongy tissue called the liver. The liver extends over the
whole of the under side of the pneumatophore, and sends processes
round the edge of the disc into the tissues of its upper surface.
Intimately associated with the liver, and penetrating its interstices, is
an organ which appears to be entirely composed of nematocysts,
derived from the ectoderm, and called the central organ. At the
margin of the disc there is a fringe of simple digitiform dactylozooids,
and between the dactylozooids and the centrally placed gastrozooid
are numerous gonozooids. Each of the gonozooids is provided with
a distinct mouth, and bears the gonophores, which escape before
the ripening of the gonads as the free-swimming Medusae called
Chrysomitra. The pneumatophore consists of a number of annular
chambers arranged in a concentric manner round the central original
chamber formed from a modified zooid. These annular chambers are
in communication with one another, and have each two pores
(pneumatopyles) opening above to the exterior. The most
remarkable feature, however, of the system is a series of fine
branching tubes ("tracheae"), which pass from the annular chambers
of the pneumatophore downwards into the hepatic mass and ramify
there.

There are two well-known genera: Velella with a sail, and Porpita
without a sail. They are both found at the surface of the warmer
regions of the great oceans and in the Mediterranean. Velella
sometimes drifts on to British coasts from the Atlantic.

The genus Discalia has a much more simple octoradial structure. It

was found at depths of 2600 and 2750 fathoms in the Pacific Ocean.

CHAPTER XII

COELENTERATA (CONTINUED): SCYPHOZOA = SCYPHOMEDUSAE

CLASS II. SCYPHOZOA = SCYPHOMEDUSAE

The Scyphozoa are jelly-fishes, usually found floating at or near the
surface of the sea. A few forms (Stauromedusae) are attached to
rocks and weeds by a stalked prolongation of the aboral region of
the umbrella. With this exception, however, they are all, in the adult
stage, of the Medusa type of structure, having a bell-shaped or
discoid umbrella, from the under surface of which depends a
manubrium bearing the mouth or (in Rhizostomata) the numerous
mouths.

Although many of the species do not exceed an inch or a few inches

in diameter, others attain a very great size, and it is among the
Scyphozoa that we find the largest individual zooids of the
Coelenterata. Some Discophora have a disc three or four feet in
diameter, and one specimen obtained by the Antarctic Expedition of
1898-1900 weighed 90 lbs.[341] The common jelly-fish, Aurelia, of
our coasts belongs to a species that appears to be very variable in
general characters as well as in size. Specimens obtained by the
"Siboga" in the Malay Archipelago ranged from 6 to 64 cm. in
diameter. The colour is very variable, shades of green, blue, brown,
and purple being conspicuous in many species; but a pale milky-blue
tint is perhaps the most prevalent, the tissues being generally less
transparent than they are in the Medusae of the Hydrozoa. The
colour of the Cubomedusae is usually yellow or brown, but
Charybdea xaymacana is colourless and transparent. The deep-sea
species, particularly the Periphyllidae, have usually an opaque
brown or dark red colour. The surface-swimming forms, such as the
common Aurelia, Pelagia, Cyanaea, are usually of a uniform pale
milky-blue or green colour. Generally the colour is uniformly
distributed, but sometimes the surface of the umbrella is freckled
with irregular brown or yellow patches, as in Dactylometra and many
others. There is frequently a special colour in the statorhabs which
renders them conspicuous in the living jelly-fish, and the lips, or parts
of the lips, of the manubrium have usually a different colour or tone
to that of the umbrella.

There is no reason to believe that the general colour of any of these

jelly-fishes has either a protective or a warning significance. Nearly
all the larger species, whether blue, green, or brown in colour, can
be easily seen from a considerable distance, and the colours are not
sufficiently bright or alarming to support the belief that they can serve
the purpose of warning either fish or birds of the presence of a
dangerous stinging animal. It is possible, however, that the brighter
spots of colour that are often noticed on the tips of the tentacles and
on the lips may act as a lure or bait in attracting small fish and
Crustacea.

Some of the Scyphozoa are phosphorescent, but it is a singular fact

that there are very few recorded observations concerning the
phosphorescence or the absence of it in most of the species. The
pale blue light of Pelagia noctiluca or P. phosphora can be
recognised from the deck of a ship in the open ocean, and they are
often the most brilliant and conspicuous of the phosphorescent
organisms.

The food of the Scyphozoa varies a good deal. Charybdea and

Periphylla, and probably many others with large mouths, will capture
and ingest relatively large fish and Crustacea; but Chrysaora
isosceles[342] apparently makes no attempt to capture either
Copepoda or small fish, but preys voraciously upon Anthomedusae,
Leptomedusae, Siphonophora, Ctenophora, and pelagic worms.
Very little is known about the food of the Rhizostomata, but the small
size of the mouths of these forms suggests that their food must also
be of minute size. The frequent association of small fish with the
larger jelly-fish is a matter of some interest that requires further
investigation. In the North Sea young whiting are the constant guests
of Cyanaea capillata.[343] Over a hundred young horse-mackerel
(Caranx trachurus) may be found sheltering under the umbrella of
Rhizostoma pulmo. As the animal floats through the water the little
fishes hover round the margin, but on the slightest alarm dart into the
sub-umbrella cavity, and ultimately seek shelter in the sub-genital
pits.[344]

Two species of fish accompany the American Medusa Dactylometra

lactea, one a Clupeoid, the other the young of the Butter-fish
(Stromateus triacanthus). According to Agassiz and Mayer[345] this is
not an ordinary case of mutualism, as the fish will tear off and devour