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Download 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 full chapter pdf scribd
Download 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 full chapter pdf scribd
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.
∗
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. Composites Science and Technology 167 (2018) 148–154
Fig. 1. TEM images of oxidized (A) and oxidized-milling (B) MWCNTs. (C) the length distributions of MWCNT-Ox after milling.
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M.A. Kazakova et al. Composites Science and Technology 167 (2018) 148–154
Table 1
The amount of adsorbed TIBA on the surface of different type MWCNTs.
Samples The amount of adsorbed TIBA
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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- of the polymer by 3–5 °C and the degree of crystallinity by 10–15% in
minosilicate minerals [43]. As it is evidenced by the formation of comparison with neat polyethylene. On the other hand, the melting
polymer films on the surface of the tubes without a clearly defined point and degree of crystallinity remain high, and the shapes of the
droplet, MWCNTs are uniformly covered by PE molecules (contact melting and crystallization peaks in the DSC curves are similar to those
angles cannot be registered, this corresponds to a high work of adhesion of the peaks of neat polyethylene. This fact indicates that the in-
of the polymer to the nanotube surface). The interaction of carbon troduction of MWCNTs into polyethylene does not lead to a significant
nanotubes with polyethylene molecules results in a surface wetting disordering of its crystal structure. So, we can suppose the existence of
with polymer, which depends strongly on both the surface composition extensive fragments of crystalline polyethylene. This observation cor-
of CNTs and the surface properties of the polymer. 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
3.2.2. In situ XRD and DSC study of MWCNT-PE composites
polymer. At the same time in situ XRD technique (due its higher sen-
The structure of all the obtained composites and neat polyethylene
sitivity) registered PE nanocrystals formation at higher temperature.
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 3.2.3. Molecular dynamics simulations of the formation of MWCNT-PE
chambers. Fig. 5 shows the typical time resolved XRD patterns of composites
MWCNT-PE composites during their melting–crystallization cycle. To qualitatively assess the formation of MWCNT-PE composites
These data allow getting accurate information on the melting and during the synthesis, the interaction of MWCNTs and PE was simulated
crystallization temperatures of PE crystal blocks within the composites using the molecular dynamics package Gromacs in the OPLS-AA force
as well as the mean size and defectiveness of PE blocks. field. The first (Fig. 7) image shows the simulated perpendicular ar-
It should be mentioned that the lattice parameter of PE crystals rangement of polyethylene molecules around the tube, which corre-
estimated from the position of the most intensive reflections (110 and sponds to the assumed primary direction of growth during the poly-
200) did not change after MWCNT incorporation into the composite. ethylene synthesis. The initial system consisted of 126 polyethylene
This corresponds to the absence of insertion of nanotube fragments molecules, and each molecule had 180 carbon atoms. The total simu-
directly into the polymer crystals. The Scherrer equation was used to lation time was 1500 ps. Eventually, structuring of polyethylene mo-
calculate of the size of coherent scattering region (CSR), which corre- lecules around the nanotube was observed. Thus, the presence of
sponds to the mean size of the ordered (crystalline) domains of PE. The MWCNTs provides the appearance of the local preferred direction of
CSR values calculated using the main intensive reflects of PE (110 and polyethylene growth and the formation of polymer lamellae oriented
200) were the same for each sample. Fig. 6 summarizes data on the along the nanotube axis. From the presented data, it is evident that
temperature dependence of CSR of PE crystals during the melting- MWCNTs contributes to the formation of extended crystal polymer due
crystallization cycles for two sets of composites. The Tcryst values esti- to wetting of nanotube by the polymer molecules.
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), 4. Discussion
which were not used for the calculations of CSR due to the low signal-
noise ratio (Fig. 6). According to in situ XRD analysis, the CSRs of neat PE (∼150 nm for
According to the DSC data (Table 3), the introduction of different 110 and 200 reflections), which was produced without nanotube ad-
type MWCNTs into the polyethylene matrix decreases the melting point 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).
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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. 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
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M.A. Kazakova et al. Composites Science and Technology 167 (2018) 148–154
Table 3
DSC and in situ XRD data of MWCNT-PE composites.
Samples MWCNT-PE composites DSC data Tmelting,°Ca DSC data Crystallinity, X% DSC data XRD data
Tcryst., °C Tcryst., °Cb
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 shaped clusters of crystallinity that grow radially from each nucleation
leads to a decrease in the relative fraction of the crystallites bound to center during crystallization. The spherulites continue to grow until
the surface of the nanotubes, and, correspondingly, to a decrease in the they reach on the adjacent the spherulites and create a spacefilling
observed average size of the polymer crystallites. In the case of neat PE, polycrystalline matrix. In the case of PE nucleation on the nanotube
the crystallite sizes increase continuously during the crystallization surface lamellae are oriented along the nanotube surface and crystallize
process. Thus, the relative volume of PE nucleated on nanotubes de- into the PE blocks covering the nanotube.
pends on their content in composite and it can be significant only for TEM images of MWCNT-PE composites produced at the early stages
the composites with high nanotube loading. of polymerization do demonstrate the formation of the polymer layers
The oxidation of MWCNTs before the catalyst deposition results in covering nanotubes. The molecular modeling also supports the or-
the formation of smaller PE crystallites (the melting curves in Fig. 6 A) ientation of PE lamellae along the nanotube surface. Nevertheless, in
as compared to the use of initial MWCNTs. The ball milling of the the case of MWCNT-PE composites, the nucleation and crystallization of
oxidized MWCNTs before the catalyst deposition results in the forma- PE crystals within the space between nanotubes is also possible during
tion of PE crystallites of the same size (the melting curves in Fig. 6 B). crystallization stage. The ratio of polymer blocks surrounding a nano-
The use of nanotubes not, milled before the catalyst deposition leads to tube and crystallized in the volume between nanotubes depends on the
the formation of PE crystallites of different size because of the diffusion concentration of MWCNTs in the composite.
limitations of ethylene polymerization within the primary aggregates of
nanotubes. 5. Conclusions
The crystallization of PE after the melting of the composites results
in the formation of PE crystallites which size depends on the MWCNT The effect of MWCNTs pre-treatment conditions, such as oxidation
content in composites. Thus, the increase in the nanotube content de- and milling, on the formation of MWCNT-PE composites by in situ
creases the polymer crystallite size (Fig. 6 A, B). polymerization technique has been investigated by in situ XRD, DSC,
These facts undoubtedly indicate that nanotubes are involved in the SEM and HRTEM. The controlled oxidation and milling treatment of
crystallization of PE molecules which are formed directly on the cata- MWCNTs increases the adsorbing ability of the TIBA-TiCl4 poly-
lyst species generated on the nanotube surface. In other words, CNTs merization catalyst system with the increased activity. It provides a
serve as the nucleating agent for PE crystallization as well as the tem- homogeneous distribution of the catalyst particles along the nanotubes
plate for the PE chain orientation. This is consistent with the data of and finally a homogeneous coverage of the nanotube surface with PE
other researchers obtained for different polymers [22] and with the molecules. For the first time, we have observed the Ti-containing cat-
results of our modeling of the interaction of PE molecules with the alyst species of the size 2–3 nm on the MWСNTs surface stabilized in the
surface of nanotubes. polymer matrix. It was found that CNTs serve as the nucleating agent
The comparison of the nucleation of PE initiated by regular nucle- for PE crystallization as well as the template for the PE chain orienta-
ating agents (NAs) [44,45] and that initiated by MWCNTs leads to the tion. The crystallization process is initiated and initially proceeds on the
conclusion that they should provide a different type of bulk organiza- nanotube surface, and then crystallites begin to form in those parts of
tion of the forming polymer crystals during the crystallization following the polymer volume that do not contact with nanotubes. Due to the
the nucleation. The nucleation caused by commercial NAs usually limited volume of the free polymer in the composites, free polymer
proceeds via the formation of lamellae nucleation centers with their crystals of a smaller size are formed. As revealed by in situ synchrotron
subsequent transformation into spherulites, which are spherically XRD, the oxidation of MWCNTs before the catalyst deposition results in
153
M.A. Kazakova et al. Composites Science and Technology 167 (2018) 148–154
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O.B. Anikeeva, E.N. Tkachev, V.I. Suslyaev, V.A. Zhuravlev, K.V. Dorozkin,
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This work (study and modeling of composites) was supported by the duced via different techniques, Phys. Status Solidi B 251 (12) (2014) 2437–2443.
Russian Science Foundation (grant 17-73-20293), composites were [26] M.A. Kazakova, N.V. Semikolenova, E.Y. Korovin, S.I. Moseenkov, A.S. Andreev,
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produced with support of the Federal Agency of Scientific polymerization technique for obtaining composite materials based on polyethylene,
Organizations Project. multi-walled carbon nanotubes and cobalt nanoparticles, Russ. J. Appl. Chem. 91
(1) (2018) 127–135.
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anti-Jewish feeling which found vent in the violent persecution of the
Jews during the years immediately preceding the conquest of the
peninsula. If so, the Spaniards by their treatment of the Jews created
the situation which they feared. The Mohammedan invasion was
prepared by the intrigues of the Jews of Spain with their co-
religionists in Africa, who exposed to the Saracens the weaknesses
of the Visigothic kingdoms. Tarik, the Mohammedan conqueror, in his
triumphant career through the peninsula, after the
711
battle of Xeres, where Roderic the last of the Visigothic
kings had fallen, was everywhere supported by the Jews. Cordova,
Granada, Malaga, and other cities were entrusted to the safe-
keeping of the Jews, and Toledo was betrayed to the invader by the
Jews, who, while the Christian inhabitants were assembled in church
praying for divine help, threw the gates open to the
712
enemy, acclaiming him as a saviour and an avenger.
Persecution had again awakened the desire for redemption,
which had never been allowed to remain dormant long.
About 720
The new Messiah appeared in the person of a Syrian
Jewish Reformer, named Serene. It so happened that the Jews of
Syria were at that time suffering almost as cruelly at the hands of the
fanatical Caliph Omar II. as at those of the Christian Emperor Leo.
When, therefore, the Messiah arose, promising to
717–720
restore them to independence and to exterminate their
enemies, many Eastern Jews lent an attentive ear to his gospel. The
Redeemer’s fame reached Spain, and the Jews of that country also,
still smarting under the sufferings of centuries and probably
disappointed in the extravagant hopes which they had built upon the
Arab conquest, hastened to enlist under his banner. But Serene’s
career was cut short by Omar II.’s successor. The Commander of the
Faithful seized the Messiah and subjected him to a severe cross-
examination. Whether it was due to the subtlety of the theological
riddles propounded to him by the Caliph, or to some more tangible
test of constancy, the Prophet’s courage failed him. It was even said,
by those who had refused to follow the Messiah, or who having
followed were disillusioned, that Serene declared his mission to be
only a practical pleasantry at the expense of his credulous co-
religionists. Be that as it may, poor Serene was delivered up to the
tender mercies of the Synagogue, and his disgrace dissipated the
Messianic dream for the time.
But in less than a generation another Reformer of the Messianic
type appeared in the Persian town of Ispahan to rekindle the
enthusiasm and try the faith of his people. This was Obaiah Abu Isa
ben Ishak. He, somewhat more modest than his predecessor,
claimed to be only one—though the last and most perfect—of a line
of five forerunners who were to prepare the way for the coming
Redeemer. He also held out the promise to free the children of Israel
from thraldom. Nor did he preach to deaf ears. One of the most
striking inconsistencies in the Jewish character is the combination
which it presents of unlimited shrewdness and suspiciousness with
an almost equal capacity for being duped. The people who in every
age have been hated as past masters of deceit, have themselves
often been the greatest victims of imposture. Religious belief is so
strong in them that, especially in times of suffering, nothing seems
improbable that agrees with their predisposition. Libenter homines id
quod volunt credunt. Ten thousand Jews rallied round Obaiah’s
standard. The war for independence began at Ispahan and for a
while seemed to promise success. But the Prophet fell in battle, and,
though his memory was kept green by his followers, who endured till
the tenth century, none proved able to carry on the work of
deliverance.
CHAPTER VI
MIDDLE AGES
This prophet and singer of Zionism died in the land which his
soul loved so dearly.
Another great Jew of Spain was Moses Maimonides, born at
Cordova in 1135. He came of a long line of Rabbis, who traced their
descent from the royal house of David, and he might be described as
a Talmudist by inheritance as well as by training. He had scarcely
completed his thirteenth year when Cordova was taken by the
fanatical sect of the Almohades, who offered to the Jews and
Christians of the city the alternatives of Islam or death. The ancient
Jewish community was broken up, and the family of Maimonides
migrated to Almeria. But this town also, three years later, fell into the
hands of the same fanatical Mohammedans, and the Jews and
Christians were once more driven forth to seek freedom of worship
elsewhere. Henceforward the family of Maimonides wandered hither
and thither through Spain, unable to find a home. But this roaming
life did not prevent the youth from attaining great proficiency in
various branches of learning, sacred and profane. His father’s
teaching was always ready at hand, and his own quick and clear
intellect found it easy to acquire and to digest the lessons of
experience. Aristotle, as has been said, was much studied, though
little understood, by the Jews and Arabs of Spain. Maimonides’
intellect had much in common with the Greek philosopher’s scientific
mind, while he possessed a sense of religion to which the Greek was
a stranger. In the character of Maimonides the two temperaments,
the Hebraic and the Hellenic, the reasoning and the emotional, met
in a harmonious combination. Truth in thought as well as in action,
was the object for which he strove, and the idle fictions of poetry
were as severely condemned by him as by the mediaeval monks;
but he was far from adopting the monastic definition of poetry as “the
Devil’s wine.” His earnestness was free from fanaticism, and he
could be severe without being savage. Unsparing in his scorn of
what he considered false, he was most forbearing towards the
victims of falsehood. Like many earnest men, Maimonides was born
a missionary. Neither fatigue of body nor pain of mind deterred him
from the diffusion of what he deemed to be the light, and to the
propagation of rational Judaism he devoted his whole life
ungrudgingly and unfalteringly. To this end he made himself master
of all the knowledge accessible in his time. He studied ancient
Paganism as well as contemporary Islam and Christianity;
philosophy, medicine, logic, mathematics, and astronomy. Thus
equipped, he entered the arena.
His people, after ten years’ wandering in Spain, had repaired to
Fez, where persecution had driven many Jews to assume the mask
of Mohammedanism—a form of compulsory hypocrisy, examples of
which abounded in every country. A zealot wrote a pamphlet
denouncing these apparent renegades as traitors to the cause of
Israel. Maimonides, who was one of them, undertook to vindicate
their conduct. But, while defending their prudence, he strove to
combat their lukewarmness, and to confirm the wavering;
endeavours which nearly cost him his life at the hands of the
Mohammedans. In the dead of night he and his family embarked on
board a vessel bound to Palestine. After a month’s perilous voyage
the refugees landed at St. Jean d’Acre (Acco), whence they
proceeded to Jerusalem, then in Christian hands, and finally reached
Egypt. There Maimonides lost his father first, and then his brother,
suffered severely in his health and fortune, and was obliged to eke
out a modest livelihood by the practice of medicine. But in the midst
of all afflictions and occupations he continued his first great work on
the Talmud, which appeared in 1168 under the characteristic title,
The Light. This work, though it failed to make its mark among the
Jews of Egypt, gradually brought fame to the author abroad. In 1175
he was already revered as a great Rabbinical authority, and
questions bearing on religion and law were submitted to him from all
parts of Israel. At the same time he busied himself with the affairs of
the Cairo community of which he was made Rabbi. In 1180 he
completed his Religious Code, in which he wedded Judaism to
philosophy. The object of the book was to introduce light and limit
into the chaos of Biblical and Talmudical teaching. The Code
attained wide popularity, and copies of it were diligently conned in
every corner of the Jewish world from India in the East to Spain in
the West. The learning as well as the character of Maimonides
excited universal respect, and many were the titles bestowed upon
the sage by his admiring co-religionists. Maimonides was proclaimed
“the Enlightener of the eyes of Israel.” Opposition and calumny, the
involuntary tributes which envy pays to success, came in due
course; but Maimonides who had not been intoxicated by praise did
not suffer himself to be intimidated by obloquy. His reputation as a
physician was almost as great as his theological renown; a
Mohammedan poet declares that “Galen’s art heals only the body,
but Maimonides’ the body and soul”; Saladin, then Vizier of Egypt,
engaged him as his physician, and Richard Coeur de Lion, who
during his crusade in the Holy Land heard of Maimonides, invited
him to be his physician in ordinary, an honour which the sage
declined. Thanks to the high esteem in which he was held by the
Mohammedan rulers of Egypt, Maimonides was, in about 1187,
made supreme and hereditary head of all the Egyptian communities.
While at the height of his power and popularity Maimonides found
himself once more exposed to the danger which he had so narrowly
escaped in Morocco. A traveller from that country recognised in the
official chief of the Hebrew community of Egypt his pseudo-
Mohammedan friend of Fez, and denounced him as an apostate.
The penalty for apostacy prescribed by the Laws of Islam is death.
Maimonides, however, succeeded in convincing the Vizier of the
Moorish visitor’s mistake, and thus was enabled to return to the calm
pursuit of his labours, communal, medical and philosophical. Soon
afterwards Palestine was re-conquered by Saladin, and the Jews
were allowed to settle in Jerusalem—a boon for which Maimonides
is supposed to be responsible.
1190 In the midst of his manifold duties, and his feud
with a rival Rabbi of Baghdad, Maimonides found time
to produce another philosophical work, the Guide to the Perplexed, a
work which forms the crown of his intellectual achievement, and
which has been pronounced “perhaps the most remarkable
45
metaphysical tour de force in the history of human thought.” At any
rate, it is a brave attempt at reconciliation between Aristotelian
philosophy and Judaic religion, between Rationalism and Revelation,
between Hellenic free-thought and Hebrew feeling. Therein is
propounded the eternal problem of the origin and destiny of things,
and solved in a manner that carried conviction at the time. The book
has, indeed, been a guide to the perplexed for many generations,
and, though it has not always commanded obedience among the
Jews, it has served as a stimulus to enquiring minds and, through
mediaeval scholasticism, has exercised an abiding influence over
Christian theology. If metaphysical speculation be of any value to
mankind, the world owes a great debt to the work of Maimonides. He
died in 1204, at the age of seventy, full of years and honours, and his
end was followed by a general outburst of grief. In Egypt both Jews
and Mohammedans held a public mourning for three days, in
Jerusalem a public fast was proclaimed, and similar funeral services
and fasts were observed in many synagogues all over the world. The
verdict of his contemporaries was, “From Moses the Prophet till
Moses Maimonides there has never appeared his equal.” Posterity
was not so unanimous in its appreciation. His tomb at Tiberias was
adorned with the epitaph: