Monika Dobrzynska-Mizera Structure and Properties of Isotactic Polypropylene Modified With Siloxane-Silsesquioxane Resin and Sorbitol...

POZNAN UNIVERSITY OF TECHNOLOGY
INSTITUTE OF MATERIALS TECHNOLOGY

Polymer Division
Monika Dobrzyoska-Mizera
Structure and properties of isotactic polypropylene

modified with siloxane-silsesquioxane resin and sorbitol
derivatives
The presented dissertation is a guide throughout monothematic series of

scientific articles realized under supervision of Prof. Tomasz Sterzyński and
Dr. Maria Laura Di Lorenzo.
POZNAO, JUNE 2017

Acknowledgements 1
Acknowledgements
While my name may be alone on the front cover of this thesis, I am by no means
its sole contributor. Rather, there is a number of people behind this piece of work who
deserve to be both acknowledged and thanked here: committed supervisors, kind
colleagues, my fantastically supportive husband and marvelous parents who lead me
here.
I am forever indebted to my academic supervisors, Prof. Tomasz Sterzyoski and

Dr. Maria Laura Di Lorenzo for their enthusiasm, guidance, and unrelenting support
throughout this process. They have routinely gone beyond their duties to fire fight my
worries, concerns and anxieties, and have worked to instill great confidence in both
myself and my work. This piece of research looks very different because of their input,
influence and expert knowledge.
I would like to thank my beloved husband Marcin for his unremitting

encouragement. Put simply, I have never met anyone who believes in me more. Thank
you for making me more than I am.
I am grateful to my parents for everything. You made me into who I am.
Also I wish to show extensive gratitude to all colleagues from Polymer Division at
Poznan University of Technology who supported me with their knowledge and kindness
from the first day we met.
Lastly, I thank all of the amazing people from Instituto per i Polimeri, Compsiti e
Biomateriali in Pozzuoli who always made me feel in Italy like at home.
1
Abstract 2
Abstract
This study details new polypropylene-based materials containing a siloxane-silsesquioxane
resin functionalized with phenyl groups and two types of sorbitol derivatives, namely 1,3:2,4-
bis(3,4-dimethylbenzylidene)sorbitol, Millad 3988 (DMDBS), and 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-
propylphenyl)methylene]nonitol sorbitol, Millad NX8000 (NX8000). The aim is to investigate the
influence of such additives on the crystallization behavior and morphology, as well as on thermal
and mechanical properties of isotactic polypropylene nucleated with the modified sorbitols, as a
function of the molecular characteristics of both the sorbitol derivative and phenyl siloxane-
silsesquioxane resin. The goal is to develop an iPP-based formulation which crystallization kinetics
is tailored to extrusion processing, in order to optimize material properties without enhancement
of production costs.
Composites based on isotactic polypropylene (iPP) modified with the sorbitol derivative
NX8000 and siloxane-silsesquioxane resin containing reactive phenyl groups (SiOPh) were
prepared by melt extrusion. The addition of sorbitol fastens crystallization kinetics of iPP and
leads to higher transparency of iPP films. Upon the incorporation of siloxane-silsesquioxane resin,
no further effect on iPP crystallization kinetics is evidenced by calorimetry, optical microscopy,
and X-ray diffraction analysis. Transparency of iPP-based composites is improved upon the
addition of sorbitol, but decreased when SiOPh is added to the formulation. The composites are
also stiffer, compared to neat polypropylene with a decreased elongation at break and increased
Young’s modulus values, with increasing amounts of fillers. The effect of the siloxane-
silsesquioxane resin on properties of iPP/NX8000/SiOPh composites was explained taking into
account compatibility of the components and morphology of the composites.
Better results were obtained upon formulation of iPP with another sorbitol derivative,
namely DMDBS, plus SiOPh. Compared to NX8000, DMDSB has varied functionalization of the
hydroxyl rings, which may affect interaction with SiOPh. Molecular adducts originating from the
synergistic interactions of siloxane-silsesquioxane resin (SiOPh) and Millad 3988 (DMDBS),
influence crystallization kinetics of isotactic polypropylene (iPP), as well as its spherulitic
morphology, transparency and mechanical properties. DMDBS is a commonly used clarifying
agent for a variety of iPP grades. However, its disadvantage is that when added into molten iPP it
allows only low draw ratios because it increases crystallization temperature of iPP. Addition of
SiOPh allows to control the nucleation efficiency of the sorbitol derivative and adjust
crystallization rate of iPP, to attain transparent formulations suitable for extrusion processes.
All presented iPP-based compounds were produced by co-rotating twin screw extrusion
and further analyzed by differential scanning calorimetry, wide-angle X-ray diffraction, scanning
electron microscopy and Fourier transform infrared spectroscopy. Moreover, rheological, haze
and static tensile measurements were conducted to determine the influence of composition on
material properties. It was found that the best combination of properties is achieved when 1 wt%
of SiOPh and 0.25 wt% DMDBS are added to iPP. This formulation can significantly change the
crystallization behavior of iPP to be tailored for production of highly oriented and transparent
products.
Further improvements were attained by addition of a compatibilizer. iPP composites
modified with NX8000 sorbitol derivative and siloxane-silsesquioxane resin (SiOPh) containing
maleated polypropylene (MAPP) as compatibilizer were prepared in order to favor interaction
between fillers. Calorimetric investigations revealed no influence of SiOPh and a slight effect of
MAPP addition on the crystallization kinetics of polypropylene. Additionally, the introduction of
2
Abstract 3
MAPP into the iPP+NX8000+SiOPh composites increased elongation at break of the samples. All
the above was attributed to the compatibilizing effect of MAPP which improved interfacial
adhesion between iPP, NX8000 and SiOPh. This phenomenon was also confirmed by the SEM
images illustrating more homogenous distribution of the filler in the compatibilized samples.
Based on the above research, formulations of iPP-based composites were tailored by
incorporation of a sorbitol derivative and a compatibilizer. Functional groups of MAPP may
suppress fibrillation of sorbitol derivative upon cooling of polypropylene and result in a control of
crystallization kinetics in iPP-based composites during production. Moreover, MAPP is
commercially available and relatively cheap in use. The addition of MAPP strongly influences
crystallization of isotactic polypropylene (iPP) as evidenced via differential scanning calorimetry
measurements. Changes in rheological properties and transparency were also examined and
turned out to be improved by the proposed modification.
3
Streszczenie 4
Streszczenie
Izotaktyczny polipropylen (iPP) jest semikrystalicznym i polimorficznym polimerem

termoplastycznym o maksymalnym stopniu krystaliczności równym 60-70%. iPP może
krystalizowad pod postacią różnych struktur krystalicznych, dlatego różnicując warunki chłodzenia
i/lub wprowadzając do osnowy polimerowej środki nukleujące możliwe jest wytworzenie różnych
morfologii w osnowie polimerowej. W rezultacie, iPP może formowad struktury zwane α, β, ,  (w
obecności komonomerów) oraz , jak i nieuporządkowaną mezofazę. Dzięki podwyższonej
transparentności oraz wyższemu modułowi elastyczności i wytrzymałości na rozciąganie, w
porównaniu z pozostałymi formami krystalicznymi, faza α jest jedną z najczęściej
wykorzystywanych.
Najczęściej wykorzystywanymi i najbardziej wydajnymi środkami nukleującymi fazę α w
izotaktycznym polipropylenie są pochodne sorbitoli. Mimo, że ich koszt jest dośd wysoki wykazują
one unikalny wpływ na właściwości optyczne. Stąd są często stosowane jako środki zwiększające
transparentnośd (claryfing agents), a żadne taosze odpowiedniki zdolne do podobnej modyfikacji
polimeru nie zostały jak dotąd opracowane. Dodatek sorbitoli skutkuje również podwyższoną
temperaturą krystalizacji oraz tworzeniem struktury drobno sferolitycznej. Pochodne sorbitoli
ulegają rozpuszczeniu w stopionym polipropylenie, co pozwala na ich skuteczne zdyspergowanie
w matrycy polimerowej podczas przetwórstwa. Podczas chłodzenia polipropylenu ze stopu,
rozpuszczony w osnowie polimerowej sorbitol przechodzi separację fazową formując sied fibryli,
która stanowi zarodki krystalizacji dla tworzonych sferolitów polipropylenu. Efekt ten ma istotne
znaczenie z aplikacyjnego punktu widzenia, ponieważ początek wzrostu krystalitów w wyższej
temperaturze pozwala na skrócenie cyklu przetwórczego, a tym samym do redukcji kosztów
produkcji np. w procesie wtryskiwania. Niemniej, zbyt duży wzrost temperatury krystalizacji, a
więc temperatury zestalania polimeru może byd wadą w przypadku wytwarzania wyrobów
wytłaczanych takich jak, folie czy włókna, ponieważ formowanie struktury następuje przed
rozpoczęciem procesu krystalizacji. W konsekwencji, przyspieszony proces krystalizacji może
ograniczad możliwośd produkcji wysoce zorientowanych wyrobów w trakcie ich chłodzenia.
W wyniku szerokich studiów literaturowych oraz wstępnych badao własnych sformułowano
następującą hipotezę realizowanej rozprawy doktorskiej. „W wyniku oddziaływania grup
fenylowych występujących w żywicy siloksanowo-silseskwioksanowej z grupami
hydroksylowymi w pochodnych sorbitoli powstają addukty, które mogą wpływad na strukturę
polimeru, a w konsekwencji na kinetykę krystalizacji oraz właściwości reologiczne i fizyczne
izotaktycznego polipropylenu.”
W ostatnich latach uwaga wielu naukowców skupiała się na tworzeniu hybrydowych
materiałów, które następnie aplikowano do matrycy polipropylenowej. Takie materiały, nazywane
modyfikowanymi silseskwioksanami (POSS), są połączeniem organicznych komponentów z
siloksanowym lub krzemowym szkieletem. Ta klasa hybrydowych materiałów posiada unikatowe
możliwości, które łączą właściwości organicznych ugrupowao z zaletami krzemowej matrycy. Co
więcej, obecnośd organicznych grup wpływa na zwiększenie hydrofobowości powierzchni cząstki,
skutkując potencjalną poprawą kompatybilności między napełniaczem, a matrycą polimerową.
Jednak, na podstawie analizy wyników badao stwierdzono, że te organiczno-nieorganiczne
materiały nie są w pełni kompatybilne z iPP. Stąd wypracowano alternatywne podejście
polegające na połączeniu komercyjnie stosowanych nukleantów z silseskwioksanami. Wykazano,
że cząsteczki silseskwioksanów modyfikowanych grupami fenylowymi, w połączeniu z sorbitolami
4
Streszczenie 5
mają możliwośd formowania złożonych adduktów poprzez wiązania wodorowe. Formowanie

struktur molekularnych zapobiega tworzeniu się sieci fibryli pochodnej sorbitolu, co ogranicza
efektywnośd nukleacji i pomaga kontrolowad proces krystalizacji polipropylenu. Niestety, wysoki
koszt syntezy POSS ograniczył możliwośd jego aplikacji, stąd nadal istnieje potrzeba poszukiwania
taoszych modyfikatorów.
Nowatorskim pomysłem jest wytworzenie modyfikatora posiadającego w swojej budowie
zarówno organiczne jak i nieorganiczne elementy, które mogą reagowad z pochodnymi sorbitolu
oraz matrycą polimerową; ich synteza jest prostsza w porównaniu z wcześniej aplikowanymi
POSS, przez co taosza w zastosowaniu. Dlatego podjęto starania mające na celu wytworzenie
nowego związku, tj. żywicy siloksanowo-silseskwioksanowej modyfikowanej grupami fenylowymi
(SiOPh). Zastosowanie takiej żywicy w połączeniu z izotaktycznym polipropylenem nukleowanym
sorbitolem nie zostało dotąd opisane w literaturze. Żywica zawierająca grupy fenylowe może
oddziaływad z grupami funkcyjnymi sorbitolu, jak również z alkilowymi grupami bocznymi, co
może wspomóc kompatybilizację z osnową polimerową.
Celem poznawczym pracy jest określenie wpływu jednoczesnego oddziaływania
pochodnych sorbitoli oraz żywicy siloksanowo-silseskwioksanowej na strukturę i właściwości
izotaktycznego polipropylenu. Do opisu interakcji występujących między modyfikatorami
zastosowano dwa rodzaje środków nukleujących, mianowicie 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-
propylphenyl)methylene]nonitol sorbitol (NX8000) oraz 1,3:2,4-bis(3,4-
dimethylbenzylidene)sorbitol (DMDBS). Związki te zawierają w swojej budowie aktywne grupy
funkcyjne, które potencjalnie mogą oddziaływad z grupami bocznymi żywicy siloksanowo-
silseskwioksanowej. Jednak ze względu na zróżnicowane rozłożenie przestrzenne grup
hydroksylowych możliwe jest tworzenie przez te związki zawad przestrzennych, które z kolei będą
wpływały na ich reaktywnośd. Stąd analiza mechanizmu tworzenia indywiduów chemicznych
między zastosowanymi w pracy modyfikatorami oraz ich wpływ na właściwości polipropylenu
wymagają wprowadzenia do osnowy polimerowej nukleantów o różnej budowie chemicznej.
Plan badao zakładał ocenę wpływu wymienionych addytywów na krystalizację i
morfologię, jak również na właściwości termiczne i mechaniczne izotaktycznego polipropylenu. W
tym celu wytworzono mieszaniny polipropylenu z dodatkiem 0,25% wag. czynnika nukleującego
oraz zawartości żywicy siloksanowo-silseskwioksanowej w zakresie od 0,1 do 3% wag. mieszane
wstępnie w mieszadle mechanicznym. Tak przygotowane składniki poddano następnie
ujednorodnianiu w procesie wytłaczania. Celem było opracowanie składu matrycy
polipropylenowej, tak aby możliwa była kontrola procesu krystalizacji polipropylenu podczas
formowania wyrobów na drodze wytłaczania w stanie stopionym, a także optymalizacja
właściwości materiału z uwzględnieniem kosztów modyfikatorów.
Analiza wstępnych wyników badao potwierdziła, że jednoczesne wprowadzenie do
izotaktycznego polipropylenu pochodnej sorbitolu DMDBS oraz żywicy siloksanowo-
silseskwioksanowej skutkuje możliwością regulowania procesu porządkowania struktury
krystalicznej osnowy polimerowej. W konsekwencji zmianie ulegają właściwości mechaniczne
izotaktycznego polipropylenu. Możliwe jest zatem stwierdzenie, że modyfikacja polipropylenu
żywicą oraz DMDBS, poprzez oddziaływania chemiczne między addytywami, wpływa na
efektywnośd nukleacji fazy α polipropylenu. Natomiast, badania optyczne wytworzonych
mieszanin potwierdziły, że dodatek SiOPh nie wpływa na pogorszenie transparentności osnowy
polimerowej. Dzięki temu możliwe jest uzyskanie wyrobów o zwiększonej transparentności i
polepszonych właściwościach wytrzymałościowych. Powyższe zostało potwierdzone na podstawie
5
Streszczenie 6
analizy wyników badao statycznej próby rozciągania, gdzie stwierdzono wzrost wartości modułu
sprężystości modyfikowanych próbek.
Nieco odmienne rezultaty uzyskano dla próbek modyfikowanych NX8000 oraz SiOPh.
Wprowadzenie NX8000 inicjuje proces porządkowania struktury polipropylenu w wyższych
temperaturach, podobnie jak w przypadku DMDBS, jednak na skutek braku oddziaływao między
nukleantem a żywicą siloksanowo-silseskwioksanową, nie zaobserwowano efektu „kontrolowanej
krystalizacji”, tj. nie odnotowano możliwości sterowania temperaturą początku procesu
porządkowania struktury krystalicznej. Stąd, w oparciu o wyniki wstępnych badao własnych
opracowano system addytywów, który oprócz NX8000 oraz SiOPh zawiera kompatybilizator w
postaci polipropylenu szczepionego z bezwodnikiem maleinowym. Stwierdzono, że takie podejście
stwarza możliwośd regulowania procesu tworzenia się specyficznej struktury krystalicznej, co
jednoznacznie przekłada się na właściwości użytkowe wyrobów.
W oparciu o studia literaturowe oraz wyniki badao własnych stwierdzono, że zaplanowane
pomiary kalorymetryczne i reologiczne oraz wybór mierzonych wielkości, takich jak: stopieo
krystaliczności, szybkośd krystalizacji, lepkośd, a także ocena transparentności czy właściwości
wytrzymałościowych, pozwoliły na opisanie zależności między charakterystycznymi parametrami a
zastosowanymi systemami modyfikującymi i szybkościami chłodzenia polimeru. Badania naukowe
w ramach realizowanej pracy doktorskiej prowadzone były w celu:
 charakterystyki żywicy siloksanowo-silseskwioksanowej,
 oceny wpływu wymienionych addytywów na krystalizację i morfologię,
 zdefiniowania struktury krystalicznej modyfikowanego polipropylenu,
 analizy właściwości optycznych i mechanicznych matrycy polimerowej modyfikowanej
sorbitolami w funkcji zawartości środków nukleujących i żywicy siloksanowo-
silseskwioksanowej oraz
 oceny właściwości reologicznych wytworzonych mieszanin polimerowych.
Wiązania chemiczne występujące w strukturze żywicy siloksanowo-silseskwioksanowej
opisano za pomocą badao metodą spektroskopii fourierowskiej, wykorzystując spektrometr FTIR
Bruker Tensor 27 pracujący w trybie ATR (Attenuated total reflectance). Natomiast, wielkośd
ziaren proszku żywicy SiOPh zmierzono przy użyciu mikroskopu skaningowego FEI Quanta 200
FEG. Ocena wpływu zastosowanych addytywów na kinetykę krystalizacji oraz morfologię
polipropylenu była możliwa dzięki zastosowaniu skaningowej kalorymetrii różnicowej (DSC) oraz
mikroskopii optycznej (MPO). Wyznaczone przy pomocy skaningowego kalorymetru różnicowego
firmy Mettler Toledo, model DSC 822, krzywe egzo oraz endotermiczne były podstawą opisu
procesów topienia oraz krystalizacji osnowy polimerowej. Ponadto, fotografie struktury oraz
pomiar szybkości wzrostu sferolitów, wykonane za pomocą mikroskopu optycznego firmy Zeiss
wyposażonego w stolik grzewczy Linkam TMHS 600, stanowiły uzupełnienie opisu procesów
topienia i krystalizacji modyfikowanej osnowy polimerowej. Fotografie SEM, wykonane przy
pomocy wyżej opisanego mikroskopu skaningowego, pozwoliły na jednoznaczne określenie
stopnia zdyspergowania modyfikatorów w osnowie polimerowej. Zweryfikowano również wpływ
zastosowanych nukleantów na strukturę izotaktycznego polipropylenu za pomocą pomiarów
prowadzonych przy użyciu dyfraktometru rentgenowskiego firmy Philips, model Analytical X-Ray
PW 1830. W celu oszacowania właściwości optycznych uzyskanych materiałów wykonano pomiary
zamglenia za pomocą urządzenia firmy Murakami Color Research Laboratory, model HM-150. To
badanie umożliwiło ocenę stopnia transparentności badanego tworzywa, a tym samym określid
jego przydatnośd pod kątem zastosowania jako materiału przeznaczonego na folie
6
Streszczenie 7
opakowaniowe. Ponadto, wykonano badania statycznej próby rozciągania z wykorzystaniem

maszyny wytrzymałościowej Instron, model 4505. Określając podstawowe właściwości
wytrzymałościowe uzyskanych kompozycji, takie jak wytrzymałośd na rozciąganie, wydłużenie przy
zerwaniu czy moduł Young’a. Wykonano także serię pomiarów reologicznych podczas chłodzenia
polimeru ze stopu mających na celu określenie wpływu modyfikatorów na temperaturę, w której
następuje gwałtowny wzrost lepkości stopu, co związane jest z początkiem procesu krystalizacji.
Przeprowadzono również analizę oddziaływao między addytywami oraz ich wpływ na strukturę
osnowy polimerowej, przy użyciu spektroskopii fourierowskiej mieszanin sorbitolu i żywicy w
stosunku 1:1, które pozwoliły na opisanie interakcji zachodzących między nimi. Zmiana
intensywności piku pochodzącego od wiązao hydroksylowych jednoznacznie świadczy o reakcji
chemicznej zachodzącej między addytywami.
Przeprowadzenie wyżej opisanego toku badao pozwoliło na weryfikację stwierdzenia
stanowiącego, że jednoczesne stosowanie pochodnych sorbitoli oraz żywicy siloksanowo-
silseskwioksanowej modyfikowanej aktywnymi grupami fenylowymi, przyczynia się do
wytwarzania transparentnych wyrobów o polepszonych właściwościach mechanicznych.
7
Foreword 8
Foreword
The presented research was conducted at Poznan University of Technology, Institute of

Materials Technology (PUT-IMT) and at Consiglio Nazionale delle Ricerche, Instituto per i Polimeri,
Compsiti e Biomateriali, Pozzuoli, Italy (CNR-IPCB), under supervision of Prof. Tomasz Sterzyoski
and Dr. Maria Laura Di Lorenzo. Prof. Sterzyoski has been supervising research work of Monika
Dobrzyoska-Mizera since she began her PhD studies. The collaboration with Dr. Di Lorenzo started
in March 2015, when Monika Dobrzyoska-Mizera spent a 3-month internship at CNR-IPCB,
between March and May 2015. This cooperation continued during the whole PhD studies of
Monika Dobrzyoska-Mizera, with several additional stages at CNR-IPCB in October 2015, April
2016, September-October 2016, and February 2017. The mutual research interest is focused on
development of novel isotactic polypropylene-based formulations with tailored properties. The
various stages at CNR-IPCB were supported by both PUT-IMT and CNR-IPCB, as well as by grants
awarded to Monika Dobrzyoska-Mizera. She received support via Erasmus+ Programme Staff
mobility for training, financed by the European Union, and she was also awarded a CNR-short-
term mobility grant to support a two-week research at CNR-IPCB, based on the proposed research
and the scientific achievements of Monika Dobrzyoska-Mizera.
The frequent visits of Monika Dobrzyoska-Mizera at CNR-IPCB and the continuation of her
research and studies at PUT-IMT, allowed to establish a joint cooperation between the two
research institutions, which has led to noteworthy results, published so far in three scientific
articles, one patent pending, and six proceedings. Further publications are in preparation.
Preliminary research, dealing with preparation of polypropylene-based composites
modified with sorbitol derivatives and silsesquioxanes, was conducted in the frame of the project
titled “Silsesquioxanes as fillers and modifiers for polymeric composites”, financed by the
European Regional Development Fund within Innovative Economy Programme. In the project,
Monika Dobrzyoska-Mizera conducted research on a new type of silsesquioxane functionalized
with phenyl groups and proved to be an efficient modifier for a sorbitol derivative. The results
have been published in five scientific manuscripts. On this basis, an application of functionalized
siloxane-silsesquioxane resin was proposed as it could potentially replace silsesquioxanes due to
its low cost synthesis procedure.
The research presented in the thesis was supported by the project “Scholarship support
for doctorate students studying at faculties perceived as strategic from Wielkopolska
development point of view”, submeasure 8.2.2. of Operational Programme “Human Resources
Development”. Italian National Research Council (CNR) Short-Term Mobility Program is also
greatly acknowledged. The author was also awarded with Etiuda doctoral scholarship, registered
as 2016/20/T/ST8/00399, funded by the National Science Center in Poland.
Milliken & Company and Chemtura are greatly acknowledged for supplying the nucleating
agent and compatibilizer samples for research.
8
Series of scientific publications 9
Series of scientific publications
The research articles numbered 1-3 concern modification of isotactic polypropylene with siloxane-
silsesquioxane resin and sorbitol derivatives. On the basis of research conducted in Ref. 1-3, a
novel polypropylene-based formulation with enhanced mechanical and optical properties was
developed and presented in a patent application (4). Preliminary research of iPP-based
compositions modified with silsesquioxanes was described in publications numbered 5-9.
1. M. Dobrzyoska-Mizera, M. Dutkiewicz, T. Sterzyoski, M. L. Di Lorenzo, Isotactic

polypropylene modified with sorbitol-based derivative and siloxane-silsesquioxane resin,
European Polymer Journal 2016, 85, 62-71. (attachment 1)
2. M. Dobrzyoska-Mizera, M. Dutkiewicz, T. Sterzyoski, M. L. Di Lorenzo, Polypropylene-
based composites containing sorbitol-based nucleating agent and siloxane-silsesquioxane
resin, Journal of Applied Polymer Science 2016, 133, 22. (attachment 2)
3. M. Dobrzyoska-Mizera, M. Dutkiewicz, T. Sterzyoski, M. L. Di Lorenzo, Interfacial
enhancement of polypropylene composites modified with sorbitol derivatives and
siloxane-silsesquioxane resin, AIP Conference Proceedings 2015, 1695, 020049.
(attachment 3)
4. M. Dobrzyoska-Mizera, T. Sterzyoski, M. L. Di Lorenzo, Kompozyt izotaktycznego
polipropylenu o kontrolowanej szybkości krystalizacji i polepszonych właściwościach
optycznych oraz sposób jego otrzymywania, patent application no. P.421623.
(attachment 4)
5. M. Barczewski, M. Dobrzyoska-Mizera, B. Dudziec, T. Sterzyoski, Influence of a sorbitol-
based nucleating agent modified with silsesquioxanes on the non-isothermal
crystallization of isotactic polypropylene, Journal of Applied Polymer Science 2014, 131, 8.
(attachment 5)
6. M. Barczewski, D. Chmielewska, M. Dobrzyoska-Mizera, B. Dudziec, T. Sterzyoski, Thermal
stability and flammability of polypropylene-silsesquioxane nanocomposites, International
Journal of Polymer Analysis and Characterization 2014, 6, 19. (attachment 6)
7. M. Barczewski, B. Dudziec, M. Dobrzyoska-Mizera, T. Sterzyoski, Synthesis and influence
of sodium benzoate silsesquioxane based nucleating agent on thermal and mechanical
properties of isotactic polypropylene, Journal of Macromolecular Science, Part A: Pure and
Applied Chemistry 2014, 11, 51. (attachment 7)
8. M. Barczewski, M. Dobrzyoska-Mizera, J. Andrzejewski, D. Chmielewska, Ocena
właściwości włókien orientowanych wykonanych z nukleowanego izotaktycznego
polipropylenu modyfikowanego silseskwioksanami, Przetwórstwo Tworzyw 2013, 3, 153.
(attachment 8)
9. M. Dobrzyoska-Mizera, M. Barczewski, B. Dudziec, T. Sterzyoski, Influence of the cooling
rate on the non-isothermal crystallization of iPP nucleated with DMDBS and
silsesquioxanes, Polimery 2013, 11/12, 58. (attachment 9)
9
Series of scientific publications 10
Proceedings
1. Kompozyty na bazie polipropylenu modyfikowane pochodną sorbitolu i żywicą

siloksanowo-silseskwioksanową, XIII Konferencja Naukowo – Techniczna „Kierunki
Modyfikacji i Zastosowao Tworzyw Polimerowych”, Rydzyna, 15-17 May 2017.
2. Analiza oddziaływao pochodnych sorbitolu z żywicą siloksanowo-silseskwioksanową na
strukturę i właściwości izotaktycznego polipropylenu, VI Konferencja Naukowa, Materiały
Polimerowe Pomerania – Plast 2016, Międzyzdroje, 7 – 10 June 2016.
3. Polypropylene-based composites containing sorbitol-based nucleating agent and siloxane-
silsesquioxane resin, The 24th Annual World Forum on Advanced Materials PolyChar 24,
Poznao, 9-13 May 2016.
4. Polypropylene-based composites containing sorbitol-based nucleating agents and
siloxane-silsesquioxane resin, The 14th Young Researchers’ Conference „Materials Science
and Engineering”, Belgrade, Serbia, 9-11 December 2015.
5. Interfacial enhancement of polypropylene composites modified with sorbitol derivatives
and siloxane-silsesquioxane resin, International conference GT70: Polymer processing
with resulting morphology and properties, Salerno, Italy, 15-17 October 2015.
6. Wpływ pochodnej sorbitolu i żywicy siloksanowo-silseskwioksanowej na szybkośd wzrostu
sferolitów izotaktycznego polipropylenu, XVIII Profesorskie Warsztaty Naukowe
Przetwórstwo Tworzyw Polimerowych, Brodowo k/Środy Wlkp., 2-4 June 2015.
7. Właściwości reologiczne izotaktycznego polipropylenu modyfikowanego sorbitolami i
silseskwioksanami, Polski Kongres Reologii, Poznao, 13 – 15 October 2013.
8. Ocena właściwości włókien orientowanych wykonanych z nukleowanego izotaktycznego
polipropylenu modyfikowanego polisilseskwioksanami, XII Konferencja Naukowo –
Techniczna „Kierunki Modyfikacji i Zastosowao Tworzyw Polimerowych”, Rydzyna, 13-15
May 2013.
9. Ocena skuteczności nukleacji izotaktycznego polipropylenu na podstawie badao
skaningowej kalorymetrii różnicowej, IV Międzyuczelniane Seminarium Studenckich Kół
Naukowych i Studiów Doktoranckich Inżynieria Wytwarzania, Kalisz, 29-30 October 2012.
Author’s contribution
The author of this dissertation prepared the propylene-based novel materials and carried out
experimental measurements to assess their properties. The research plan, developed by the
author of this dissertation, included several experimental techniques: Differential Scanning
Calorimetry (DSC), Scanning Electron Microscopy (SEM), Optical Microscopy (POM), rheology,
Fourier Transform Infrared Spectroscopy (FTIR), Wide-Angle X-Ray Diffraction (WAXD), haze and
static tensile measurements. Moreover, she conducted literature review, as well as critical
analysis and interpretation of the experimental data. Both the research plan and publications of
the main results were supervised by Prof. Tomasz Sterzyoski and Dr. Maria Laura Di Lorenzo.
10
List of abbreviations 11
List of abbreviations
DMDBS 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol
DSC Differential Scanning Calorimetry
FTIR Fourier Transform Infrared Spectroscopy
iPP Isotactic polypropylene
MAPP polypropylene-graft-maleic anhydride
NX8000 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol sorbitol
POM Polarized Optical Microscopy
SiOPh Siloxane-silsesquioxane resin modified with phenyl groups
SEM Scanning Electron Microscopy
WAXD Wide-Angle X-Ray Diffraction
11
Table of content 12
Table of content
Acknowledgements ............................................................................................................................ 1
Abstract .............................................................................................................................................. 2
Streszczenie ........................................................................................................................................ 4
Foreword ............................................................................................................................................ 8
Series of scientific publications .......................................................................................................... 9
Proceedings ................................................................................................................................. 10
Author’s contribution .................................................................................................................. 10
List of abbreviations ......................................................................................................................... 11
Table of content ............................................................................................................................... 12
1. Introduction ................................................................................................................................ 14
2. Experimental ............................................................................................................................... 16
2.1 Materials ............................................................................................................................... 16
2.2 Preparation of SiOPh ............................................................................................................. 16
2.3 Sample preparation ............................................................................................................... 17
2.4 Methodology ......................................................................................................................... 18
2.4.1 Scanning Electron Microscopy (SEM)............................................................................ 18
2.4.2 Differential Scanning Calorimetry (DSC) ....................................................................... 18
2.4.3 Polarized Optical Microscopy (POM) ............................................................................ 18
2.4.4 Oscillatory Rheological Measurements ........................................................................ 19
2.4.5 Fourier Transform Infrared Spectroscopy (FTIR) .......................................................... 19
2.4.6 Wide-Angle X-ray Diffraction (WAXD)........................................................................... 19
2.4.7 Haze............................................................................................................................... 19
2.4.8 Static Tensile Tests ........................................................................................................ 19
3. Results and discussion .................................................................................................................. 20
3.1 Structure and crystallization behavior .................................................................................. 20
3.2 Rheological properties .......................................................................................................... 27
3.3 Intermolecular interactions................................................................................................... 29
3.4 Crystal phases in polypropylene ........................................................................................... 30
3.5 Performance of iPP-based composites ................................................................................. 31
3.6 Interfacial enhancement of iPP-based composites............................................................... 35
3.6.1 Structure analysis .......................................................................................................... 36
3.6.2 Performance of compatibilized composites ................................................................. 37
12
Table of content 13
3.7 Commercial iPP-based composites with controlled crystallization rate and enhanced
transparency .................................................................................................................................. 39
4. Conclusions ..................................................................................................................................41
5. Literature......................................................................................................................................42
Attachment 1.....................................................................................................................................45
Attachment 2.....................................................................................................................................46
Attachment 3.....................................................................................................................................47
Attachment 4.....................................................................................................................................48
Attachment 5.....................................................................................................................................49
Attachment 6.....................................................................................................................................50
Attachment 7.....................................................................................................................................51
Attachment 8.....................................................................................................................................52
Attachment 9.....................................................................................................................................53
13
Introduction 14
1. Introduction
Isotactic polypropylene (iPP) is one of the most widely used thermoplastic polymer due to
its good mechanical properties, low cost and ease of processing [1-3]. Similar to other
semicrystalline polymers, its properties depend on crystal fraction, crystal morphology, as well as
on crystal modification. iPP can develop various crystal forms called α-, β-, -, and ε-structures, as
well as a conformationally disordered mesophase [4-21]. -crystal modification of polypropylene
is industrially significant as it reveals good thermomechanical properties and high impact
resistance [5,12,13,21+. However, the α-structure is the most important polymorph from
commercial point of view, since it ensures to iPP better transparency as well as higher modulus
and tensile strength, compared to the other crystal modifications [24-25]. iPP processing and
formulation can be tailored to obtain the crystal structure and morphology, for instance by
varying crystallization conditions and/or introduction of nucleating agents into the polymeric
matrix.
Sorbitol derivatives are extensively used clarifiers to obtain transparent iPP products due
to their high efficiency [22-23, 26]. Although the cost of sorbitol derivatives is relatively high, their
effect on polypropylene transparency is unique, not attainable by other cheaper nucleating
agents actually available. Moreover, the addition of sorbitol derivatives results in the beginning of
polypropylene crystallization at higher temperatures. They melt at processing temperature of
polypropylene and form a fibrillar network upon polymer cooling. This creates fine, homogenous
dispersion of spherulites with minimalized scattering of light, which is crucial for applications
[27,28]. Furthermore, it is an advantage during injection molding, as crystallization at higher
temperature allows to shorten the cycle time, thus reduce production cost. Conversely, it is
detrimental in case of extrusion, because too intense nucleation limits production of oriented
goods, such as films and fibers, since these products can be shaped exclusively prior to
crystallization, i.e. before formation of spherulitic structure [29]. Hence, if crystallization occurs at
too high temperature, only limited stretching can be applied during extrusion.
For this reason, large research efforts are devoted to sorbitol modifiers capable of
controlling crystallization process of nucleated polypropylene. It was proved that the addition of
silsesquioxanes (POSS), being cage-like organosilicon compounds functionalized with phenyl side
groups, to polypropylene matrix nucleated with a sorbitol derivative allowed to stretch
polypropylene with higher draw ratios during extrusion [30-34]. Silanol silsesquioxane and the
sorbitol derivative, namely di(benzylidene)sorbitol, are capable of forming several complex
molecular adducts, thanks to noncovalent hydrogen bonding. This partially interferes with
fibrillation of the sorbitol derivative upon cooling and in turn allows to tailor crystallization of iPP
[35]. Unfortunately, the very high cost of commercial POSS has limited its use so far, and there is
still a need to seek for lower cost modifiers.
As an effort to find lower cost modifiers able to control crystallization of polypropylene
containing sorbitol derivatives, a novel siloxane-silsesquioxane resin (SiOPh) was synthesized in
our laboratory. Siloxane-silsesquioxane resins can be easily modified with functional groups
similar to POSS and can potentially replace silsesquioxanes thanks to their much lower cost [36-
39]. The siloxane-silsesquioxane resin that we used as additive to iPP nucleated with sorbitol,
contains silanol groups as well as side alkyl groups, as illustrated in Figure 1, below. The silanol
groups are expected to interact with the functional groups of sorbitol [30], and the side alkyl
groups may promote blending with polyolefins [40]. Thus, the addition of SiOPh into nucleated
14
Introduction 15
iPP may allow to lower crystallization temperature compared to iPP/sorbitol only, while
preserving the clarifying effect gained upon the addition of the sorbitol derivative. This in turn will
provide iPP-based products with enhanced transparency and anisotropic mechanical properties.
To our knowledge, SiOPh has never been used as additive to iPP/sorbitol, as no patent was
issued/deposited, and no research results have been published in the literature on silimar
formulations.
The influence of a newly developed siloxane-silsesquioxane resin with phenyl groups, on
properties of iPP containing a commercial sorbitol derivatives, namely 1,3:2,4-bis(3,4-
dimethylbenzylidene)sorbitol, Millad 3988 (DMDBS) and 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-
propylphenyl)methylene]nonitol sorbitol (NX8000), are presented in this PhD thesis. Since the
modifiers contain free hydroxyl groups, able to create mutual molecular adducts, they are
expected to suppress fibrillation of percolated network of sorbitol derivative upon cooling of
polypropylene [35]. This allows for tailoring the crystallization process of polypropylene matrix
and enables production of transparent, highly oriented films or fibers. Compared to NX8000,
DMDSB has varied functionalization of the hydroxyl rings, which may affect interaction with
SiOPh. The influence of both additives on the crystallization under static and shearing conditions,
as well as morphology, mechanical and optical properties of iPP were investigated.
The aim of the research work detailed in this thesis is to investigate the influence of such
additives on the crystallization behavior and morphology, as well as on thermal and mechanical
properties of isotactic polypropylene nucleated with the modified sorbitol, as a function of the
molecular characteristics of both the sorbitol derivative and phenyl siloxane-silsesquioxane
resin. The goal is to develop an iPP-based formulation which crystallization kinetics is tailored to
extrusion processing, which is needed to optimize material properties taking into account
production costs as well.
15
Experimental 16
2. Experimental
2.1 Materials
A commercial iPP, Midilena III PPF401, with MFR = 3 g/10 min (230C, 2.16 kg) from
Rompetrol Petrochemicals S.R.L. (Romania) was used. The selected iPP grade is characterized by a
low modification level, i.e. there are no plasticizers, colored masterbatches or nucleating agents
added, which is an ideal formulation to investigate the effect of nucleating agents and other
additives on properties of iPP.
Two sorbitol derivatives were selected as additives for iPP: 1,3:2,4-bis(3,4-
dimethylbenzylidene)sorbitol, Millad 3988 (DMDBS) and 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-
propylphenyl)methylene]nonitol sorbitol, Millad NX8000 (NX8000), both were kindly provided by
Milliken Chemical Company (Belgium, USA). Previous investigations revealed that 0.25 wt% is a
sufficient amount of sorbitol able to promote -crystal nucleation in isotactic polypropylene [41-
43]. Siloxane-silsesquioxane resin modified with phenyl groups of general formula [PhSiO1.5]n,
abbreviated SiOPh, was synthesized in our laboratory as detailed below. The thermal stability of
all materials was determined using thermogravimetry (TGA), which proved that all the
components do not undergo thermal degradation at the used processing temperatures of iPP. The
chemical formulas of DMDBS and NX8000 are presented in Figure 2.1.
(a) (b)
Fig. 2.1 Chemical structures of (a) DMDBS, (b) NX8000
2.2 Preparation of SiOPh
The synthesis was conducted using two-step acid-base co-condensation of

tetraethoxysilane and phenyltriethoxysilane mixture in 2:1 molar ratio. Tetraethoxysilane,
phenyltriethoxysilane and tetrahydrofuran (THF), in an amount of twice the volume of the silanes
used, were placed in a flask equipped with a mechanical stirrer. The solution was stirred for 30
min to homogenize the ingredients. Then, an aqueous solution of hydrochloric acid in water (1.5
mL of 35.5% HCl in 100 mL of water) was added into the solution of silanes in THF in order to
acidify the reaction medium. Once the acid was added, the reaction mixture became turbid. After
about 15 min, turbidity disappeared and a rise in temperature occurred. Stirring was maintained
for 60 min to cool down the mixture to room temperature. Next, aqueous ammonia solution was
added dropwise in order to basify the reaction medium (3.5 mL of 25% aqueous ammonia in 200
mL of water). Upon the addition of alkali, the mixture underwent turbidity again (formation of the
product). After the addition was completed, an intensive stirring was maintained for additional 60
16
Experimental 17
min. Afterwards, the mixture was filtered, washed twice with 100 ml of water and dried for 24
hours at 120°C. The chemical formula of SiOPh is presented in Figure 2.2.
Fig. 2.2 Chemical structure of SiOPh
2.3 Sample preparation
Polypropylene pellets were milled into powder in a Tria high-speed grinder. Polymer was
mixed with the sorbitol derivatives and SiOPh in the rotary mixer Retsch GM 200 for 3 min at a
rotation speed of 3000 rpm. Homogenization of the premixed compositions with different SiOPh
contents (0.1 – 3 wt%) and a fixed sorbitol concentration of 0.25 wt% was ensured by molten
state extrusion with a Zamak corotating twin screw extruder operated at 190C and 70 rpm. The
extruded rod was pelletized in a water bath. iPP/sorbitol/SiOPh composites at various
compositions were prepared, as summarized in Table 2.1.
Table 2.1 Designations and mass concentrations of samples

Mass concentration [%]
iPP DMDBS SiOPh iPP NX8000 SiOPh

iPP 100 0 0 iPP 100 0 0
iPP+DMDBS 99.75 0.25 0 iPP+NX8000 99.75 0.25 0
iPP+DM+0.1SiOPh 99.65 0.25 0.1 iPP+NX+0.1SiOPh 99.65 0.25 0.1
iPP+DM+0.5SiOPh 99.25 0.25 0.5 iPP+NX+0.5SiOPh 99.25 0.25 0.5
iPP+DM +1SiOPh 98.75 0.25 1 iPP+NX+1SiOPh 98.75 0.25 1
iPP+DM +1.5SiOPh 98.25 0.25 1.5 iPP+NX+3SiOPh 96.75 0.25 3
The composites were compression-molded with a Collin Hydraulic Laboratory Forming

Press P 200 E at a temperature of 200°C, firstly without any pressure applied to allow complete
melting (3 min), followed by exerting a pressure of about 10 MPa for another 3 min, then cooled
to room temperature in less than 3 min by means of cold water circulating in the plates of the
press. iPP-based sheets with a thickness of 150 µm and 1.2 mm were obtained. The thin films
were used for the study of crystallization rate, to limit the effect of thermal gradients within the
sample during the phase transition, whereas the thick films were used for the investigation of
mechanical properties of the materials, to comply with ISO standards [44].
17
Experimental 18
2.4 Methodology
2.4.1 Scanning Electron Microscopy (SEM)

Morphological analysis of cryogenically fractured iPP/sorbitol/SiOPh composites was
performed using a FEI Quanta 200 FEG environmental scanning electron microscope (ESEM)
(Eindhoven, The Netherlands) in low vacuum mode, using a Large Field Detector (LFD) and an
accelerating voltage of 10-20 kV. Before analysis, the samples were sputtered-coated with Au-Pd
alloy using Baltech Med 020 Sputter Coater System, then mounted on aluminum stubs.
2.4.2 Differential Scanning Calorimetry (DSC)

The thermal properties of iPP and its composites were investigated using a Mettler DSC
822 calorimeter, Mettler-Toledo, Inc., equipped with a liquid-nitrogen accessory for fast cooling.
The calorimeter was calibrated in temperature and energy using indium. Dry nitrogen was used as
purge gas at a rate of 30 ml/min.
In order to set the structure for the analysis of crystallization kinetics, each sample was
heated from 25 to 200°C at a rate of 20°C min-1, melted at 200°C for 10 minutes to erase previous
thermal history, quickly cooled to 160° at 20°C min-1 to limit as much as possible the exposure to
high temperatures, then cooled at various rates, ranging from 0.5 to 4°Cmin-1.
Crystallization is an exothermic process, and the heat evolved during the phase transition
may cause thermal gradients within the sample. As a consequence, transitions can occur at
temperatures that do not correspond to those detected by the instrumentation [45,46]. The
thicker the sample, the more critical this problem is. In order to reduce these issues, sample mass
was limited to 3.0 ± 0.2 mg, and cooling rates not exceeding 4°C min-1 were used (compare with
2.3).
2.4.3 Polarized Optical Microscopy (POM)

Spherulite growth rates were estimated by optical microscopy, using a Zeiss polarizing
microscope equipped with a Linkam TMHS 600 hot stage. A small piece of compression-molded
sample was squeezed between two microscope slides, then inserted in the hot stage. The
thickness of the squeezed sample was lower than 10 m. The radius of the growing crystals was
monitored during solidification by taking photomicrographs at appropriate intervals of time, using
a Scion Corporation CFW-1312C Digital Camera. Spherulite radii were measured with the software
Image-Pro Plus 7.0.
The temperature program before isothermal and non-isothermal crystallizations were
identical to those used in calorimetry. For non-isothermal crystallization, a self-nucleation
procedure was used, in order to expand the temperature range of analysis. Each sample was
heated from 25 to 200°C at a rate of 20°C min-1, melted at 200°C for 10 minutes to erase previous
thermal history, cooled to 155°C at 30°C min-1, and maintained at 155°C until the appearance of
the first crystals. Then, the temperature was raised to 160°C by heating at 30°C min-1, equilibrated
at 160°C, then the samples were cooled at 0.5°C min-1 until spherulite impingement [47].
Isothermal crystallization measurements at 150C and 153C were also conducted, to
confirm reliability of the data gained using the non-isothermal procedure.
18
Experimental 19
2.4.4 Oscillatory Rheological Measurements

An MCR Anton Paar rheometer with a plate diameter of 25 mm operating in the plate-
plate configurations under the oscillatory shear mode with a frequency  = 10 rad s-1 and a strain
of 1%, was used in the rheological investigations. In each experiment the sample was melted at
220°C and held at for 10 min to erase memories of previous processing, as well as to reduce the
internal stress associated to sample preparation. Afterward, the sample was cooled to the final
temperature of 100°C at a constant cooling rate  = 4 °C min-1. Crystallization was monitored using
the oscillatory shear mode [48,49].
2.4.5 Fourier Transform Infrared Spectroscopy (FTIR)

Infrared spectra of pure SiOPh were collected with a Bruker Tensor 27 FTIR spectrometer
in ATR mode using 16 scans. The spectra resolution was 2 cm-1. Sample specimens were measured
as obtained, without additional preparation steps.
The IR spectra were also collected with a Bruker Vertex 70 FTIR spectrometer in absorption mode
using 64 scans. The spectra resolution was 1 cm-1. Sample specimens were prepared by mixing
SiOPh and DMDBS with milled potassium bromide (KBr). This powder was then compressed under
vacuum into thin pellets using a pressure of 20 MPa. Four different mixtures were examined by
FTIR. The first and second samples were prepared at ambient temperature using pure SiOPh and
DMDBS, respectively. The other specimens were mixtures of SiOPh and DMDBS with a ratio of
1 : 1. For the tests, one sample was kept at ambient temperature and the second was heated to
190C. All of the spectra were submitted to a weather correction, including the correction for CO2
[50-52].
2.4.6 Wide-Angle X-ray Diffraction (WAXD)

WAXD measurements were performed on a Philips Analytical X-Ray, model PW 1830
diffractometer with Cu Kα radiation. The scanned 2θ range was from 2 to 45 with a scanning rate
of 0.02 and time per step of 1 s. The samples used for WAXS analysis were in the form of
compression molded sheets of 1.2 mm thickness. Characteristic peaks were assigned according to
the literature [7,16,53].
2.4.7 Haze
The optical behavior of the polymers was characterized by haze measurements carried
out on the 150 µm compression molded films according to the PN-84/C-89100 standard [54] using
a Haze Meter HM-150 produced by Murakami Color Research Laboratory (Japan).
2.4.8 Static Tensile Tests

Mechanical properties of iPP-based compression-molded sheets were evaluated as per
ISO 52732 using Instron tensile tester, model 4505. Measurements of elastic modulus were
conducted at a crosshead speed of 1 mm min-1, to ensure deformation rate close to 1% of
measuring section length per minute [44]. Elongation at break was estimated at a speed of 50 mm
min-1 for a reasonable duration of the experiments [55,56].
19
3. Results and discussion 20
3. Results and discussion
3.1 Structure and crystallization behavior
Structure and morphology of the novel phenyl siloxane-silsesquioxane resin, synthesized

in both University in Poznao and CNR laboratories, were investigated by electron microscopy and
infrared spectroscopy. The SEM micrograph displayed in Fig. 3.1 shows spherical SiOPh particles
with a diameter of approximately 1µm. It is also seen from the image that a sufficient size
distribution of the particles was achieved using the two-step acid-base condensation method
detailed above.
Fig. 3.1 SEM micrograph showing morphology of SiOPh particles
Figure 3.2 presents the FTIR spectrum of the SiOPh resin. All bands in the FTIR spectrum
confirm the structure of the obtained material. Broad bands at 3627 and 3390 cm -1 are attributed
to the presence of silanol groups (respectively free OH and hydrogen-bonded ones). The band at
954cm-1 characteristic for SiOH groups is also observed in the spectrum. The bands at 1631 and
571cm-1 indices minor hydratation of the sample. The presence of phenyl groups is confirmed by
the presence of stretching vibrations of CH, C=C (3075, 3054, 1595 and 1431 cm-1, respectively)
as well as bending vibrations of =CH bonds at 789, 738 and 697 cm-1. A high intensity band, with
two maxima at 1130 and 1049 cm-1, results from stretching vibrations of SiOSi bands and is
characteristic for silicon materials [57]. The maximum at 1049 cm-1 indicates the presence of
smaller stretching of SiOSi bands (<144) and the one at 1130 cm-1 confirms those of about
144. This split in oscillation region is related to the transverse and longitudinal valence
oscillations of the atoms in siloxane bridge so the frequencies of the mentioned oscillations are
distributed in separate regions from 1010 to 1140 cm-1 and 1190 to 1300 cm-1 in the range of θ
from 120 to 180° *58]. This split can also be attributed to the simultaneous presence of Q and T
units in the examined structure. The Q unit represents a silicon atom linked through siloxane
bond to subsequent four silicon atoms forming a tetrahedron. Wherein, the T unit presents a
silicon atom bonded to further three silicon atoms and one phenyl group [59]. The low intensity
bands characteristic for stretching vibrations of CH bonds (sp3 CH3 and sp2 CH2 groups) at about
2979 and 2929 cm-1 appeared due to the presence of small amount of unreacted (not hydrolyzed)
20
ethoxy groups. Obtaining such a structure, that is siloxane-silsesquioxane resin with POSS Q
structures as network nodes with reactive phenyl groups in siloxane bridges between
silsesquioxane (POSS) molecules, allows for replacement of expensive functionalized
silsesquioxanes with this cheaper compound. Moreover, resin containing Q POSS units and
reactive functional groups is, in principle, capable to interact with organic polymers and sorbitol
derivatives, which has been studied in-depth and results are presented in this thesis.
Fig. 3.2 FTIR spectrum of SiOPh resin
To gain information about the phase structure and morphology of the iPP composites
containing sorbitols and resin, scanning electron microscopy analyses were performed. The
results are presented in Figure 3.3 and 3.4 Figures 3.3-a and 3.4-a illustrate the cryogenically-
fractured surface of compression-molded plain iPP, which appears quite smooth as expected.
Morphology of iPP composite containing 0.25 wt% of NX8000 is exhibited in Figure 3.3-b. The
fractured surface is quite smooth and similar to the one shown in Figure 3.3-a, with only small
particles that adhere on iPP surface, possibly revealing the presence of sorbitol. The latter
appears well distributed within iPP, thorough the analyzed area. The fractured surface
morphology changes drastically upon addition of SiOPh, as illustrated in Figure 3.3-c, which
presents the scanning electron micrograph of the sample containing 3 wt% of resin. A number of
large voids of various dimensions are visible on the sample surface, possibly due to filler particles
that are pulled out upon the cryogenically fracture process. At the same time some nearly
spherical particles, attached to the iPP matrix also appear. The size of both the holes and particles
indicates considerable filler agglomeration upon melt processing, since the average particle size of
unprocessed SiOPh is ~1µm, as shown in Figure 3.1, much smaller that the spheres and voids seen
in Figure 3.3-c.
21
Fig. 3.3 SEM micrographs for iPP (a), iPP+NX8000 (b), iPP+NX+3SiOPh (c)
Polypropylene nucleated with DMDBS reveals denser network of lines visible on sample
surface (Fig. 3.4-b). Morphology seems to be homogeneous as the nucleating agent well dissolves
in iPP while processing [28]. However, small spherulite size and minute amount of DMDBS added
do not allow to distinguish particular components in the fractured sample presented in SEM
micrograph. Figure 3.4-c illustrates morphology of the composite containing both modifiers,
which significantly differs from the fractured surfaces shown in Figures 3.4 and 3,4-b. Their
average diameter is about 1 m, which well compares with the average size of the as-synthesized
SiOPh. This indicates that negligible agglomeration of the fillers occurred upon melt processing of
iPP/DMDBS/SiOPh composites. The modifier is nicely distributed and attached to the studied
surface, which reveals good distribution of the filler within the sample.
Fig. 3.4 SEM micrographs for iPP (a), iPP+DMDBS (b), iPP+DM+1.5SiOPh (c)
Calorimetric studies were realized by differential scanning calorimetry measurements at

four different cooling rates, to obtain in-depth information on the crystallization behavior of iPP
composites. The raw DSC curves for the cooling rate of 4C/min are presented in Fig. 3.5-a and
3.6-a. Plain iPP starts its crystallization at 129C, when cooled at 4C/min. Upon the addition of
DMDBS and NX8000 sorbitol derivatives the onset of crystallization is shifted towards higher
temperatures, i.e. to 138C and 137C, respectively. This proves that both sorbitol derivatives
enhance nucleation of iPP spherulites, which occurs at higher temperatures, as expected
[19,28,42].
Addition of the siloxane-silsesquioxane resin to iPP/DMDBS formulation slightly reduces

the crystallization temperature of iPP, compared to the one containing iPP and DMDBS only. A
significant decrease of the crystallization temperature range occurs in the presence of 1.5 wt% of
22
SiOPh, as seen in Figure 3.5-a. The influence of SiOPh/DMDBS composition on nucleation

efficiency of DMDBS is quantified in Fig. 3.5-b, which presents the DSC onset temperature of
crystallization as a function of the cooling rate. The onset point was taken as the intersection of
the baseline before the transition and the inflectional tangent and the peak temperature as the
maximum of the exotherm [60]. As seen in Figure 3.5-b, the onset of the phase transition shifts
towards higher temperatures with decreasing cooling rate , as typical for polymer crystallization:
lower  ensures more time to overcome the energy barriers for nucleation [45]. More
importantly, at parity of cooling rate, compared to iPP containing DMDBS only, increasing
amounts of SiOPh induce crystallization to start at progressively lower temperatures, indicating
that the presence of the siloxane-silsesquioxane resin significantly affects nucleating efficiency of
the sorbitol derivative, with a content of 1.5 wt% of SiOPh being the most effective one.
(a)
(b)
Fig. 3.5 DSC crystallization curves and the onset temperature versus cooling rates
The addition of 0.25 wt% of NX8000 sorbitol induces crystallization to start at high
temperatures compared to plain iPP. Further incorporation of 0.1 to 3 wt% of SiOPh into
iPP/NX8000 does not induce significant variations in the crystallization profile of iPP nucleated
with sorbitol, as all the DSC curves shown in Figure 3.6-a practically overlap, within experimental
23
error. The onset temperatures of the analyzed composites are plotted in Figure 3.6-b as function
of the cooling rate. In polymer samples containing added particles, for a given cooling rate, the
temperature at which crystallization starts is indicative of the effectiveness of the filler to
promote heterogeneous nucleation [61,62].
(a)
(b)
Fig. 3.6 DSC crystallization curves and the onset crystallization temperature versus cooling rates
Sorbitol clarifiers dissolve in molten iPP and thereby, distributes homogenously during
processing through the whole volume of polymeric matrix. As proposed in Ref. [41,63,64],
intermolecular hydrogen bonding and π_π interactions between the adjacent phenyl rings are
established upon cooling, and sorbitol crystallizes with development of a percolated fibrillar
network that facilitates growth of polypropylene spherulites [28]. As mentioned above, the
increased crystallization temperature of the iPP/sorbitol composites proves that 0.25 wt% is a
sufficient amount to allow precipitation of sorbitol upon cooling. Progressive addition of SiOPh
into iPP/DMDBS formulation causes a corresponding delay in crystallization, quantified in Figure
3.5. Instead, when the siloxane-silsesquioxane resin is added to the iPP/NX8000 formulation, the
nucleation efficiency is not affected. Both sorbitols and SiOPh, which structures are depicted in
24
Figures 2.1 and 2.2, have functional groups that may in principle interact upon melt mixing, by
possible establishment of hydrogen bonds, influencing miscibility of the modified sorbitol with
polypropylene and in turn, its efficiency as nucleating agent [30]. It was proved [35] that the fibrils
of sorbitol derivatives have higher affinity to molecules modified with silanol groups. However, for
all the analyzed compositions containing NX8000 and various amounts of SiOPh, the onset
temperature is not affected by SiOPh, as shown in Figure 3.6-b. This indicates that limited or
negligible interaction between NX8000 and SiOPh is established, and the modified sorbitol
maintains its efficiency as nucleating agent for isotactic polypropylene, independently of resin
content, at least for the analyzed composition range. On the other hand, some kind of interplay
between DMDBS and SiOPh is established, however the modified sorbitol maintains its efficiency
as nucleating agent for isotactic polypropylene, at least for the analyzed composition range, i.e.
below 1.5 wt% of SiOPh.
Tables 3.1 and 3.2 summarize characteristic values obtained during non-isothermal
crystallization of iPP composites. The onset temperatures are pictured in Figures 3.5-b and 3.6-b,
hence are not repeated in Tables 3.1 and 3.2, which only show the peak temperatures (Tp) and
crystallinity degrees (Xc).
Table 3.1 Crystallization temperature peaks (Tp) of iPP-based formulations cooled at the indicated
rates
Cooling rate [C/min] Cooling rate [C/min]

4 2 1 0.5 4 2 1 0.5
iPP 127.0 129.5 132.5 135.5 iPP 127.0 129.5 132.5 135.5
iPP+DMDBS 134.5 137.0 139.0 141.0 iPP+NX8000 134.5 136.5 138.0 139.5
iPP+DM+0.1SiOPh 134.0 136.5 139.0 141.0 iPP+NX+0.1SiOPh 134.0 136.5 138.5 140.5
iPP+DM+0.5SiOPh 133.5 135.5 138.0 141.0 iPP+NX+0.5SiOPh 134.5 136.5 138.0 139.5
iPP+DM+1SiOPh 133.5 135.5 136.0 139.0 iPP+NX+1SiOPh 134.0 136.0 138.0 140.0
iPP+DM+1.5SiOPh 127.5 131.5 134.0 136.0 iPP+NX+3SiOPh 134.5 136.0 138.0 139.5
The crystallinity degree values were calculated from the data obtained from the DSC plots, gained
during cooling at different rates, according to the following equation (3.1):
-
(3.1)
where HM is the experimental heat of fusion, H0 is the enthalpy of fusion of the fully crystalline
polymer, equal to 207.1 Jg-1 [65], and  is the weight fraction of the modifiers. As reported in
Table 3.2, the crystal fraction developed upon cooling at rates up to 4°Cmin-1 is Xc = 50  3%,
independently of composite composition. This indicates that the addition of sorbitol only, or
coupled with up to 3 wt% of SiOPh, does not affect crystallinity of polypropylene, under the
chosen experimental conditions. It influences only crystallization kinetics of iPP, as the onset and
peak points are shifted to higher temperatures due to enhanced nucleation of iPP spherulites.
25
Table 3.2 Crystallinity (Xc) of iPP-based formulations cooled at the indicated rates
Cooling rate [C/min] Cooling rate [C/min]

4 2 1 0.5 4 2 1 0.5
iPP 51 48 48 53 iPP 51 49 48 54
iPP+DMDBS 50 50 50 51 iPP+NX8000 50 52 50 53
iPP+DM+0.1SiOPh 52 49 49 51 iPP+NX+0.1SiOPh 51 51 51 53
iPP+DM+0.5SiOPh 52 47 47 47 iPP+NX+0.5SiOPh 51 50 48 52
iPP+DM+1SiOPh 52 49 49 51 iPP+NX+1SiOPh 50 49 51 51
iPP+DM+1.5SiOPh 47 50 50 48 iPP+NX+3SiOPh 51 51 53 52
Polarized Optical Microscopy (POM) was used to estimate the spherulite growth rate (G)
of iPP and its composites with sorbitols and resin. In order to gain data in a wide temperature
range, non-isothermal crystallization experiments were performed using a self-nucleation
procedure [46]. Such method was chosen because of the high density of nucleation of the
samples that contain sorbitol: at low temperatures high number of very small spherulites grow
simultaneously, which hinders reliable analysis of the rate of their growth. Conversely, with self-
nucleation and measurements upon continuous cooling, experiments are made when only a few
iPP spherulites grow; they can reach relatively large dimensions, which permits reliable data
analysis until impingement.
The measurements were conducted at a constant cooling rate so G can be estimated by
taking the first derivative of the radius (r) vs. temperature (T) plot at each experimental point:
(3.2)
where dr/dT is a measured point from the plot and dT/dt is the cooling rate [66].
Figure 3.7 represents the spherulite growth rate vs. temperature plots for iPP/NX8000
samples. The data overlap, within experimental error, in all the analyzed temperature range,
showing that the growth rate of iPP spherulites is not affected by addition of the fillers. During
crystallization, the dispersed sorbitol and silicate particles must be rejected and/or occluded by
the growing spherulites, which in principle can disturb spherulite growth: energy needs to be
dissipated to reject, engulf or deform the non-crystallizable additives, but likely such energy
barrier is quite low and results in a negligible contribution to spherulite growth rate.
26
Fig. 3.7 Spherulite growth rates of iPP and its composites measured upon cooling from the melt
at 0.5C min-1
3.2 Rheological properties
Differential scanning calorimetry data provided information on crystallization upon

quiescent cooling from the melt. Further information were gained by oscillatory rheological
measurements conducted during cooling, to evaluate the effect on viscosity changes under
shearing conditions. Fig.3.8 shows the values of complex viscosity as a function of temperature for
samples containing different amounts of SiOPh and a fixed content of sorbitol derivative of 0.25
wt% (see Table 2.1). The differences between nucleated and non-nucleated iPP are significant in
terms of the crystallization behavior. The onset of crystallization in unfilled polypropylene is
induced from a sudden and abrupt increase in complex viscosity at 130C. In case of the nucleated
samples, the onset of dynamic viscosity appears earlier during cooling, prior to crystallization of
plain iPP, and increases due to the fibrillar network formation of sorbitol [65,67]. In contrast, an
increasing SiOPh content in iPP/DMDBS formulations leads to a decrease in the viscosity growth
that was caused by DMDBS nucleation effect. In case of the addition of 1.5 wt% of SiOPh, an
overall suppression of primary DMDBS activity is observed. Looking at the sample containing 1
wt% of SiOPh, a different crystallization behavior is observed. Despite the fact that the interaction
between SiOPh and DMDBS leads to the removal of an early onset viscosity increase, the
nucleation efficiency was only slightly reduced as also proved by DSC measurements.
As evidenced by DSC, upon cooling at 4°C/min the iPP/DMDBS sample that contains
1 wt% of SiOPh starts to crystallize at 137C, which coincides with rheology results. It is worth
noting that DSC analysis reveals crystallization of iPP under static conditions. Conversely,
rheological measurements determine complex viscosity of formulation under shear, which
significantly increases upon crystallization of sorbitol fibrillar network (Fig. 3.8). This allows to
more efficiently simulate processing conditions and possibly predict the influence of siloxane-
silsesquioxane resin on formation of sorbitol network upon processing. Addition of SiOPh
significantly influences establishment of sorbitol fibrillar network, which is expected to grow upon
cooling. The addition of 1 wt% of SiOPh moved the beginning of fibrillar network formation
towards lower crystallization temperature by over 15C. This feature might be crucial especially
27
for production of oriented goods, such as films and fibers. During extrusion process, the molten
polymer is initially shaped in a die, then it is further stretched in order to enhance its anisotropic
mechanical properties. The latter can be attained exclusively before occurrence of crystallization.
Introduction of SiOPh into iPP/DMDBS formulation shifts the onset of crystallization towards
lower temperatures, thus extending the time available for stretching. This phenomenon allows to
apply higher draw ratios and in turn improve anisotropic mechanical properties of oriented
products.
Fig. 3.8 Complex viscosity curves vs. temperature obtained during cooling of nucleated iPP
modified with different amount of SiOPh ( = 4C min-1)
Fig.3.9 shows the values of complex viscosity as a function of temperature for iPP
formulations containing different amounts of SiOPh and a fixed content of NX8000 of 0.25 wt%.
The onset of crystallization of neat polypropylene is evidenced at 130C. In case of the nucleated
sample, the crystallization is moved towards higher temperatures, due to nucleation ability of
NX8000 added into formulation. An increasing SiOPh amount does not induce significant
variations in the crystallization profile of iPP-based composites, as all the rheological curves
shown in Figure 3.9 practically overlap, within experimental error.
Fig. 3.9 Complex viscosity curves vs. temperature obtained during cooling of iPP modified with
NX8000 and different amounts of SiOPh ( = 4C min-1)
28
3.3 Intermolecular interactions
Studies of crystallization of iPP modified with both the DMDBS sorbitol derivative and
siloxane-silsesquioxane resin by DSC and oscillatory rheology indicate possible interactions
between the fillers. Moreover, literature data indicate that even small amount of silsesquiaxane
functionalized with phenyl groups may interfere in formation of DMDBS fibrillar network upon iPP
cooling from a molten state [30,35]. As mentioned before, siloxane-silsesquioxane resin contains
such functional groups, hence possible interactions between DMDBS and SiOPh need to be
studied. Such interactions may lead to suppression of fibrillar network formation which is
supposed to be maintained by the formation of hydrogen bonds between –OH groups included in
the sorbitol derivative. Possible interaction between functional groups of the two fillers was
investigated by FTIR [35].
The FTIR spectra of neat DMDBS and SiOPh are presented in Figure 3.10-a. In DMDBS, a
broad O–H stretching peak is observed at wavenumbers of 3189 and 3139 cm-1, and peaks at a
wavenumber of 2900 cm-1 are associated with CH2 and CH3 groups. A separate peak at 1247
cm-1 is assigned to C–O stretching group. The FTIR spectrum of pure SiOPh shows broad bands at
3613 and 3130 cm-1, which are attributed to the presence of silanol groups (respectively free -OH
and hydrogen bonded ones). Moreover, aromatic C–H stretching is detected at a wavenumber of
3021 cm-1. The presence of phenyl groups is confirmed by the stretching vibrations of C = C at
1597 and 1400 cm-1. A high intensity band, with two maxima at 1135 and 1080 cm -1, results from
stretching vibrations of Si–O–Si bands and is characteristic for silicon materials [57]. The band at
954 cm-1 characteristic for Si–OH groups is also observed in the spectrum.
(a) (b)
Fig. 3.10 FTIR spectra of (a) neat siloxane-silsesquioxane resin and sorbitol derivative and (b)
DMDBS and SiOPh mixtures at ambient and processing temperatures
SiOPh–DMDBS mixtures were examined to infer possible hydrogen bonding between the two
modifiers used in the study. The two powdered fillers were mixed at room temperature, where no
interaction between functional groups are expected [35], as well at the temperature used for melt
processing of the composites (190°C). The FTIR spectra of the two mixtures are compared in
Figure 3.10-b. The O–H stretching peak of Si–OH group in siloxane-silsesquioxane resin is found at
3130 cm-1 while the one originating from C–OH stretching group in DMDBS is at 3189 cm-1. The
height of O–H stretching was controlled as its lower intensity would indicate an interaction
between DMDBS and siloxane-silsesquioxane resin. Figure 3.10-b presents O–H stretching peak of
29
the heated sample which lowers its intensity proving occurrence of possible interaction. For this
reason, areas under O–H stretching peaks for both mixtures, at ambient temperature and heated
to processing temperature, were used for calculations according to equation (3.3) [57,68-69]:
( ) (3.3)
where: absorbance O–H is the area of the signal of O–H groups. A comparison of the peak areas
allows for assessing a change in number of available O–H groups. Substituting peak areas to the
equation (3.3) revealed that the heated sample possesses about 4% less available O–H groups in
comparison to the mixture at ambient temperature. This indicates considerable weakening of the
hydrogen bonds between the DMDBS particles and consequently overlap of the interactions
between the DMDBS and SiOPh molecules. In other words, interactions between the DMDBS and
SiOPh molecules possibly occur via hydrogen bonding [35], which may lead to an interference in
DMDBS fibrillation, and in turn vary its nucleation efficiency.
3.4 Crystal phases in polypropylene
Wide-angle X-ray diffraction (WAXD) analyses were performed particularly to determine

an effect of the additives on possible phase transitions in isotactic polypropylene. Figure 3.11
presents WAXD spectra of representative samples of pure iPP, iPP nucleated with sorbitol
derivatives and iPP containing both sorbitol derivative and SiOPh resin. Distinct and sharp
reflections are observed for all samples at 2θ = 14.1, 16.9, 18.5, 21.2 and 21.8, corresponding
to (110), (040), (130), (111) and (041) respectively, which are characteristic for α phase [7].
Moreover, it is proved that β and  phases do not appear in the samples as no additional peaks at
16.2° and 19.8° were noticed [7,9]. The crystal fraction measured by WAXD is also unaffected by
addition of sorbitol and silicate, in agreement with the DSC results detailed above. Hence, the
additives do not modify crystal structure of isotactic polypropylene, at least for the analyzed
compositions and thermal history. An influence of processing conditions on iPP-based composites
structure as well as their crystal size will be detailed in a forthcoming manuscript.
(a) (b)
Fig. 3.11 WAXS patterns of pure and modified polypropylene with (a) DMDBS and SiOPh
and (b) NX8000 and SiOPh
30
3.5 Performance of iPP-based composites
The sizably effects of the fillers on crystallization of iPP, detailed above, are expected to
influence also optical and mechanical properties. In isotactic polypropylene, similarly to other
semicrystalline polymers, light scattered on the bigger units of their structure makes the products
opaque [70]. Often the size of the crystalline units is large enough to interfere with visible light
and this interference results in considerable haze. Haze is associated with a loss of contrast due to
light scattering at large angles, and is defined as the total flux of light scattered within the angular
range between 2.5° and 90° and normalized to the total transmitted flux [71].
The influence of sorbitol derivative and siloxane-silsesquioxane resin on haze of
polypropylene films is presented in Figure 3.12. The addition of nucleating agent results in a
significant decrease in haze values, which means that the nucleated sample is more transparent in
comparison with pure iPP. Gradual addition of SiOPh only slightly reduces transparency of
polymeric matrix, as seen in Figure 3.12. These data parallel the variation in crystallization of iPP
upon addition of the two modifiers, where precipitated sorbitol serves as substrate for the growth
of iPP spherulites, whose number is enhanced and their size is reduced in the formulations
containing DMDBS and SiOPh [72]. The size of the spherulites depends on composition. Addition
of SiOPh resin to the composite that contains also DMDBS alters fibrillation of percolated network
of sorbitol, which smoothens its nucleating efficiency. As lowering spherulite size improves
transparency of the material, only slightly worsened optical properties in the formulations
containing both fillers were obtained, however they still remain transparent enough to ensure
their applicability as e.g. packaging products.
Fig. 3.12 Dependence of haze on SiOPh concentration in iPP/DMDBS composites for compression-
molded sheets with thickness of 150 m
The effect of NX8000 and SiOPh resin upon haze of iPP is presented in Figure 3.13.
Introduction of sorbitol derivative results in a significant decrease in the haze value, which
indicates that the nucleated sample was more transparent than pure iPP. However, the gradual
addition of SiOPh results in worsening of matrix transparency, wherein the addition of 1wt% and
more results in haze values similar or higher than this for pure matrix. As shown by Horvath et al.
[72], crystallinity, spherulite size, lamella thickness, and probably also the interface area between
31
the crystalline and amorphous phases may play a significant role in haze values. However, the
principal parameter influencing haze is the spherulite size of the supermolecular structure formed
during crystallization of polymer, wherein haze decreases with decreasing spherulite size. As
mentioned above, together with an increasing content of siloxane-silsesquioxane resin, a
significant deterioration in transparency occurs. As evidenced in the SEM micrograph presented in
Fig. 3.3, in iPP/NX8000/SiOPh composites the addition of SiOPh results in considerable filler
agglomeration upon melt processing, thus agglomerates may interfere with visible light and result
in a significant decrease in transparency.
Fig. 3.13 Dependence of haze on SiOPh concentration in iPP/NX8000 composite for compression-
molded sheets
Mechanical properties of the iPP/DMDBS/SiOPh composites were determined using static

tensile tests. Main results are summarized in Figure 3.14. A qualitative change in the stress-strain
behavior was noted for all the compositions, since the samples that contain either DMDBS only or
both modifiers do not undergo yielding. The composition dependence of elastic modulus (E),
reported in Figure 3.14-a, reveals an increase in E for the nucleated sample in comparison to the
pure one, from 1.25 to 1.45 GPa, and further decrease to a value of 1.3 GPa for the sample
containing the highest amount of SiOPh modifier. On the contrary, the addition of sorbitol
derivative results in a decrease in the elongation at break (r) value, from r = 600% for pure
polypropylene, down to r = 150% for the sample containing sorbitols, in agreement with
literature data reported by other authors [73-75]. However, the elongation at break somewhat
increases with the addition of siloxane-silsesquioxane resin, up to r = 250%, as shown in Figure
3.14, which suggests a somewhat improvement of mechanical performance of the composites,
compared to the formulation containing iPP and DMDBS only.
As detailed in the literature [77] there are two mechanisms of crack propagation in α
polypropylene during a uniaxial tensile test: crazes appear at the center of spherulite, grow
parallel to a radial direction and eventually reorient their propagation direction perpendicularly to
the tensile axis. Alternatively, in some cases the flaws are initialized at the spherulite boundary.
Both mechanisms lead to the formation of major cracks affecting mechanical behavior of the
samples. Introduction of DMDBS into iPP results in creation of bigger amount of smaller
32
spherulites and drastically increases the total length of spherulite boundaries. All the above ease
crack propagation in -nucleated samples, hence they reveal more brittle character. The addition
of siloxane-silsesquioxane resin causes partial reduction of nucleating efficiency of the sorbitol,
hence larger iPP spherulites grow in the presence of SiOPh, which in turn leads to slightly higher
elongation at break values.
(a)
(b)
Fig. 3.14 Mechanical properties of pure, nucleated with DMDBS and modified with SiOPh
polypropylene matrix; (a) Young’s modulus and (b) elongation at break (the lines were drawn to
guide the eye)
Mechanical properties of the iPP/NX8000/SiOPh composites are summarized in Figure

3.15. Analysis of changes in the elastic modulus, reported in Figure 3.15-a, reveals a slight
increase in this value for the nucleated sample in comparison to the pure one, from 1.25 to 1.35
GPa, and further rise to a maximum value of 1.56 GPa for the sample that contains the highest
amount of modifiers. On the contrary, the addition of sorbitol derivative and an increasing
amount of siloxane-silsesquioxane resin results in a continuous decrease in the elongation at
break values, from 600% for pure polypropylene, down to 14% for the iPP+NX+3SiOPh sample.
Moreover, a qualitative change in the stress-strain behavior was noted, since the samples that
contain siloxane-silsesquioxane resin do not undergo yielding.
33
The mechanical properties of semicrystalline polymer composites depend markedly on

composition and phase structure, as well as on crystal fraction, size and morphology. Some
slightly increased lamellae thickness can be expected from the increased crystallization
temperature, in the nucleated samples, but no variation in crystal fraction, nor crystal
modification was probed by DSC and WAXS analyses. Adhesion between the filler and the matrix
largely affects the large strain properties such as the elongation at break, whereas the low-strain
properties, like Young’s modulus, are much less dependent on compatibilization of the
components, being mostly additive [78]. As seen in Figure 3.3, the SiOPh particles create
agglomerates which are poorly bonded to the iPP matrix, thus behave as voids in the structure
that facilitate premature fracture upon deformation, which leads to a decreased elongation at
break with increasing amounts of the filler. Aggregates in the structure are formed due to
chemical affinity of SiOPh particles and a lack of interfacial interaction between the siloxane-
silsesquioxane resin and NX8000 sorbitol. In case of iPP/DMDBS/SiOPh composites a converse
effect takes place, i.e. SiOPh particles act reciprocally with DMDBS which prevents formation of
SiOPh clusters. Moreover, the resin interferes with precipitation of sorbitol fibrillar network upon
cooling of polypropylene. This ensures uniform distribution of the fillers in polymeric matrix and
significantly influences crystallization behavior, therefore it influences mechanical properties of
the compositions.
(a)
(b)
Fig. 3.15 Mechanical properties of pure, nucleated with NX8000 and modified with SiOPh
polypropylene matrix; (a) Young’s modulus and (b) elongation at break (the lines were drawn to
guide the eye)
34
3.6 Interfacial enhancement of iPP-based composites
Besides benefits of the resin on control of crystallization kinetics of iPP, which was the
primary aim of the research work detailed in this thesis, an unfavorable influence of SiOPh on
some properties of the obtained composites, e.g. elongation at break, was noted in case of
iPP/NX8000 composites. As an effort to improve material properties, a compatibilizer was
introduced into the formulation. The selected compound is a polypropylene-graft-maleic
anhydride (MAPP) copolymer, which is a commercial and low cost compatibilizer, commonly used
to improve interfacial adhesion in blend/composites of polypropylene with polar additives.
Polybond 3150 produced by Chemtura (United Kingdom) was used, which has maleic anhydride
content of 0.5 wt%. Its chemical structure is presented in Fig. 3.16.
Fig. 3.16. Chemical structure of polypropylene-graft-maleic anhydride (MAPP) [79]
Polyolefin-based composites are often modified with both organic and synthetic fillers
[80-86]. Although, modified composites may offer many advantages, a major disadvantage is a
lack of compatibility between the matrix and filler. This complicates the achievement of good
dispersion and strong interfacial adhesion [87-88], which can lead to poor performance of the
final product. This may be overcome by introduction of adhesion promoters, which can favor
interaction between the filler and matrix. This approach is applied in this research, in order to
enhance interactions between the sorbitol derivative and siloxane-silsesquioxane resin. The aim is
to investigate the influence of the coupling agent on mechanical properties and crystallization
behavior of isotactic polypropylene nucleated with sorbitol derivative and containing various
amounts of siloxane-silsesquioxane resin. iPP/NX8000/SiOPh/MAPP blends at various
compositions were prepared, as summarized in Table 3.3.
Table 3.3 Designations and mass concentrations of compatibilized samples

NX8000 SiOPh MAPP
iPP+NX8000+MAPP 0.25 0 5
iPP+NX+0.5SiOPh+MAPP 0.25 0.5 5
iPP+NX+1SiOPh+MAPP 0.25 1 5
iPP+NX+3SiOPh+MAPP 0.25 3 5
35
3.6.1 Structure analysis
To gain information about the phase structure and morphology of compatibilized iPP
composites containing sorbitol, resin and compatibilizer, scanning electron microscopy analyses
were performed. The results are presented in Figure 3.17. Figure 3.17-a represents the
cryogenically-fractured surface of compression-molded pure polypropylene, which appears quite
smooth. Small inclusions in Figure 3.17-b are dispersed agglomerations of sorbitol derivative,
however the particles seem well dispersed within iPP. Remarkable changes are visible in Figure
3.17-c, where the fractured surface of the composite containing 3 wt% of resin displays hollows
and particles of various size. This is caused by resin agglomeration and its poor adhesion to
polymeric matrix. This poor morphology can be improved by addition of 5 wt% of compatibilizer,
which enhances the interaction between the matrix and filler and results in smoother structure,
as seen in Fig. 3.17-d. The latter formulation still presents visible inclusions of different size that
probably are agglomerates of siloxane-silsesquioxane resin, but the size distribution of the
particles is much more homogeneous, with a largely enhanced adhesion of the filler to the matrix.
These remarkable changes in morphology are expected to favorably affect mechanical properties
of the composites.
Fig. 3.17 SEM micrographs for iPP (a), iPP+NX8000 (b), iPP+NX+3SiOPh (c),
iPP+NX+3SiOPh+MAPP (d)
36
3.6.2 Performance of compatibilized composites
To assess the influence of resin and binder addition on mechanical properties of iPP, static
tensile tests were conducted. The results for samples with and without compatibilizer are
presented in Fig. 3.18. The addition of MAPP results in a remarkable increase in plastic properties
for all studied samples. In case of nucleated polypropylene, an increase in the elongation at break,
from 220%, for iPP+NX8000, up to 300%, for iPP+NX+MAPP, is noted. Even more promising results
are obtained for the samples that contain siloxane-silsesquioxane resin and MAPP binder. The
elongation at break values for the compatibilized samples that contain 0.5, 1 and 3 wt % of SiOPh
are respectively 7, 5, and 2.5 times higher in comparison to the composites without MAPP.
Addition of MAPP influences adhesion between matrix and filler throughout interaction with the
organic –OH groups available on the surface which then adhere to matrix by linking molecular
chains [89-90]. The analysis reveals that the more SiOPh was added, the smaller increase in the
elongation at break is noted which indicates that the amount of compatibilizer may need to be
adjusted as a function of SiOPh content, taking into account a varied amount of active hydroxyl
groups.
Fig. 3.18 Elongation at break of polypropylene and its composites compatibilized with MAPP
Non-isothermal crystallization kinetics was investigated by differential scanning calorimetry

(DSC) at four different cooling rates, ranging between 0.5 and 4C/min, to provide information on
crystallization process. The values of crystallization (TC) and onset (Tonset) temperatures
determined from crystallization peaks for all studied samples are summarized in Table 3.4 and
Figure 3.19.
37
Table 3.4 Crystallization peak (Tc) and onset (Tonset) temperatures for compatibilized samples upon
cooling at various cooling rates 
Tc [C] vs.  [C/min] Tonset [C] vs.  [C/min]

4 2 1 0.5 4 2 1 0.5
iPP 127.0 129.5 132.5 135.5 iPP 129.0 132.0 135.0 138.0
iPP+NX8000 134.5 136.5 138.0 139.5 iPP+NX8000 137.0 139.0 141.0 143.0
iPP+NX+MAPP 132.0 134.0 136.0 138.5 iPP+NX+MAPP 134.0 138.0 139.0 142.0
iPP+NX+0.5SiOPh 131.5 134.0 136.5 138.5 iPP+NX+0.5SiOPh
+MAPP +MAPP
133.5 137.5 140.0 142.5
iPP+NX+1SiOPh 131.0 133.0 137.0 138.5 iPP+NX+1SiOPh

+MAPP +MAPP
133.5 136.5 141.0 142.0
iPP+NX+3SiOPh 132.0 133.0 135.0 138.5 iPP+NX+3SiOPh

+MAPP +MAPP
136.0 135.5 137.0 141.5
As stated above, the addition of 0.25 wt% of sorbitol derivative results in a sizeable increase of
TC and Tonset, proving its efficiency as nucleating agent. Upon the addition of compatibilizer in the
formulation, a slight decrease of TC by about 1-3C is noted, depending on cooling rate and
composition. This may be explained by an interaction between binder and sorbitol derivative
through –OH groups, which affects miscibility of the sorbitol derivative with iPP and its
precipitation and consequent creation of three-dimensional network of sorbitol fibrils that act as
nucleation sites for iPP. Further addition of siloxane-silsesquioxane resin into system, regardless
the amount, does not affect nucleation efficiency of the blends.
Fig. 3.19 DSC crystallization curves of iPP/NX8000/MAPP samples upon cooling at 4 °C/min
38
3.7 Commercial iPP-based composites with controlled crystallization rate and

enhanced transparency
Siloxane-silsesquioxane resin used in the study contains phenyl functional groups which
interact with functional groups of sorbitol derivatives. This leads to suppression of fibrillar
network formation which is supposed to be maintained by creation of hydrogen bonds between
–OH groups included in the sorbitol derivative. Since industry is permanently seeking for solutions
able to reduce production costs and meet customers’ requirements, it was proposed to produce
iPP-based composites containing sorbitol derivative and compatibilizer only. Functional groups
included in polypropylene-graft-maleic anhydride may in principle suppress fibrillation of sorbitol
derivative upon cooling of polypropylene and result in a control of crystallization kinetics in iPP-
based composites during production. The chemical coupling agent Polybond 3150, with MFR = 50
g/10 min (230C, 2.16 kg), and 0.5 wt % of maleic anhydride, abbreviated MAPP, kindly provided
by Chemtura (UK), was used. iPP/DMDBS/MAPP blends at various compositions were prepared, as
summarized in Table 3.5.
Table 3.5 Designations and mass concentrations of iPP/DMDBS/MAPP samples

iPP DMDBS MAPP
iPP 100 0 0
iPP+DMDBS 99.75 0.25 0
iPP+DM+5MAPP 94.75 0.25 5
iPP+DM+10MAPP 89.75 0.25 10
Calorimetric studies were realized by differential scanning calorimetry measurements at

four different cooling rates, to obtain in-depth information on the crystallization behavior of iPP
composites. The raw DSC curves for the cooling rate of 4C/min are presented in Fig. 3.20. Plain
iPP starts its crystallization at 133.5C, when cooled at 4C/min. Upon the addition of DMDBS
sorbitol derivative the onset of crystallization is shifted towards higher temperatures. Addition of
the compatibilizer into iPP/DMDBS formulation slightly reduces the crystallization temperature of
iPP, compared to the one containing iPP and DMDBS only. A significant decrease of the
crystallization range occurs in the presence of 10 wt% of MAPP, as seen in Figure 3.20. Compared
to iPP containing DMDBS only, increasing amounts of MAPP induce crystallization to start at
progressively lower temperatures, indicating that the presence of the polypropylene-graft- maleic
anhydride significantly affects nucleating efficiency of the sorbitol derivative.
39
Fig. 3.20 DSC crystallization curves of iPP/DMDBS/MAPP samples upon cooling at 4 °C/min.
Further information were gained by oscillatory rheological measurements conducted

during cooling, to evaluate the effect on viscosity changes under shearing conditions. Rheological
measurements determine complex viscosity of formulation under shear, which significantly
increases upon crystallization (Fig. 3.21). This allows to more efficiently simulate processing
conditions and possibly predict the influence of compatibilizer on formation of the sorbitol
network that nucleates iPP. Addition of MAPP significantly influences establishment of sorbitol
fibrillar network, which is expected to grow upon cooling. The addition of 10 wt% of MAPP moves
the beginning of fibrillar network formation towards lower crystallization temperature by about
10C. This feature might be crucial especially during extrusion process where molten polymer is
initially shaped in a die, then it is further stretched in order to enhance its anisotropic mechanical
properties. Introduction of MAPP into iPP/DMDBS formulation shifts the onset of crystallization
towards lower temperatures, thus extending the time available for stretching. This phenomenon
allows to apply higher draw ratios and in turn improve anisotropic mechanical properties of
oriented products [91].
Fig. 3.21 Complex viscosity curves vs. temperature obtained during cooling of nucleated iPP
modified with different amounts of compatibilizer ( = 4C min-1)
40
Conclusions 41
The effect of DMDBS and MAPP upon haze of iPP is presented in Figure 3.22. Introduction
of sorbitol derivative results in a significant decrease in the haze value, which indicates that the
nucleated sample is more transparent than pure iPP. Gradual addition of MAPP maintains
transparency of polymeric matrix, as seen in Figure 3.22. These data parallel the variation in
crystallization of iPP upon addition of the two modifiers, where precipitated sorbitol serves as
substrate for the growth of iPP spherulites, whose number is enhanced and their size is reduced in
the formulations containing DMDBS and MAPP [72]. The modified samples remain transparent
enough to ensure their applicability as e.g. packaging products.
Fig. 3.22 Dependence of haze on MAPP concentration in iPP/DMDBS composites for compression-
molded sheets with thickness of 150 m
4. Conclusions
This study details how a combination of the sorbitol derivatives and functionalized
siloxane-silsesquioxane resin influences properties of iPP-based composites. The synthesis of
newly proposed SiOPh is substantially easier and cheaper, in comparison to previously studied
POSS molecules, ensuring their possible replacement as additives to iPP.
Addition of the sorbitol derivatives to iPP results in increased crystallization temperature

and smaller spherulite diameter, due to enhanced nucleation density. Further incorporation of
SiOPh into iPP/DMDBS formulation affects formation of sorbitol fibrillar network, due to
synergistic interaction between active functional groups of both modifiers. Hence, transparency is
improved upon the addition of DMDBS, and not further affected by incorporation of SiOPh. The
nucleated samples are stiffer, with a decreased elongation at break and increased Young’s
modulus upon addition of sorbitol-based modifier. Changes in mechanical properties of
iPP/DMDBS samples are attributed to interaction between –OH groups present in both modifiers.
Hence, combining isotactic polypropylene with DMDBS and siloxane-silsesquioxane resin allows to
obtain iPP with enhanced anisotropic mechanical and optical properties. Therefore, a new iPP-
based formulation containing DMDBS and siloxane-silsesquioxane resin, with an optimum amount
41
Literature 42
of 0.25 wt% of DMDBS and 1 wt% of SiOPh, has been developed. This formulation may be
especially suitable for extrusion processes.
Incorporation of SiOPh into the polypropylene matrix already modified with NX8000 does
not affect nucleation kinetics of iPP -spherulites, nor the rate of their growth. Transparency is
improved upon the addition of NX8000, but somewhat worsened with increasing content of resin.
The iPP/NX8000/SiOPh samples are stiffer, with a decreasing elongation at break and increasing
Young’s modulus values, with increasing amounts of fillers in the composites. This behavior is
attributed to a poor interaction between iPP, NX8000 and/or siloxane-silsesquioxane resin. Such a
result is somewhat unexpected, since in principle interactions between the –OH groups present in
both modifiers could be predicted. In order to enhance chemical interactions between the
modifiers used in the system, an addition of compatibilizer being polypropylene-graft-maleic
anhydride has been proposed.
Incorporation of the compatibilizer favors interactions between the composite

components resulting in much better dispersion and interfacial bonding between the fillers and
iPP matrix. The addition of MAPP greatly improves the elongation at break values of iPP blends,
even seven times for the iPP+NX+0.5SiOPh+MAPP sample. Crystallization kinetics is slightly
changed upon the addition of compatibilizer, probably because the latter partially interferes with
precipitation of sorbitol with formation of three-dimensional structure.
It has been found that the utilization of the sorbitol nucleating agent in association with
polypropylene-graft-maleic anhydride (MAPP) only, improves properties such as good clarity of
polypropylene and formation of smaller polypropylene spherulites, simultaneously allowing for
controlled crystallization of polypropylene. These improvements can be utilized in commercial
production of transparent polypropylene films with enhanced mechanical properties. Since, these
novel iPP-based formulations have large commercial potential, a patent application has been
submitted.
5. Literature
[1] J. Varga, J. Mater. Sci. 27 (1992) 10.
[2] M. Gahleitner, C. Tranninger, P. Doshev, J. Appl. Polym. Sci. (2013) 39626.
[3] G. Chen, B. Feng, K. Zhu, Y. Zhao, X. Yuan, Chem. Res. Chin. Univ. 31 (2015) 2.
[4] G. Natta, P. Corradini, Nuovo. Cim. 15 (1960) 1.
*5+ S. Brückner, S.V. Meille, V. Petraccone, B. Pirozzi, Prog. Polym. Sci. 16 (1991) 361.
*6+ S.V. Meille, S. Brückner, Nature 340 (1989) 6233.
*7+ S.V. Meille, D.R. Ferro, S. Brückner, A.J. Lovinger, F.J. Padden, Macromolecules 27 (1994) 9.
[8] B. Lotz, J.C. Wittmann, A.J. Lovinger, Polymer 37 (1996) 4979.
[9] A. Turner-Jones, J.M. Aizlewood, D.R. Beckett, Makromol. Chem. 75 (1964) 1.
[10] F.J. Padden, H.D. Keith, J. Appl. Phys. 30 (1959) 1479.
[11] B. Lotz, Macromolecules 47 (2014) 7612.
[12] M. Cocca, R. Androsch, M.C. Righetti, M. Malinconico, M.L. Di Lorenzo, J. Mol. Struct. 1078
(2014) 114.
[13] J. Garbarczyk, D. Paukszta, Colloid Polym. Sci. 263 (1985) 12.
[14] J. Garbarczyk, T. Sterzyoski, D. Paukszta, Polym. Commun. 30 (1989) 5.
[15] J. Garbarczyk, D. Paukszta, S. Borysiak, J. Macromol. Sci. Phys. 41 B (2002) 4-6.
42
Literature 43
[16] D. Paukszta, J. Garbarczyk, Fibres. Text. East. Eur. 11 (2003) 5.

[17] D. Hybiak, J. Garbarczyk, Polymers 7-8 (2014) 585.
[18] D. Hybiak, S. Chmielewska, J. Garbarczyk, Polymers 11-12 (2015) 700.
[19] A. Romankiewicz, T. Sterzyoski, W. Brostow, Polym. Int. 53 (2004) 12.
[20] T. Sterzyoski, H. Øysæd, Polym. Eng. Sci. 44 (2004) 2.
[21] T. Sterzyoski, P. Calo, M. Lambla, M. Thomas, Polym. Eng. Sci. 37 (1997) 12.
[22] A. Romankiewicz, J. Jurga, T. Sterzynski, Macromol. Symp. 202 (2003) 281-290.
*23+ T. Sterzyoski, Polymers 45 (2000) 11-12.
[24] M. Raab, J. Scudla, J. Kolarik, Eur. Polym. J. 40 (2004) 1317.
[25] E.P. Moore, Polypropylene handbook. Polymerization, Characterization, Properties,
Processing, Applications., Hanser, Munich, 1996.
[26] A. Thierry, C. Straupe, J.C. Wittmann, B. Lotz, Macromol. Symp. 241 (2006) 1.
[27] M. Gahleitner, C. Grein, S. Kheirandish, J. Wolfschwenger, Intern. Polym Proc. 26 (2011) 2-20.
[28] M. Kristiansen, M. Werner, T. Tervoort, P. Smith, Macromolecules 36 (2003) 5150.
[29] R. Pantani, I. Coccorullo, V. Volpe, G. Titomanlio, Macromolecules 43 (2010) 9030.
[30] M. Barczewski, M. Dobrzyoska-Mizera, B. Dudziec, T. Sterzyoski, J. Appl. Polym. Sci. (2014)
40131.
[31] S. Roy, V. Scionti, S.C. Jana, C. Wesdemiotis, A.M. Pischera, M.P. Espe, Macromolecules
(2011) 44.
[32] S. Roy, S.C. Jana, Antec. Conf. Proc. 69 (2011) 1105.
[33] S.C. Jana, J.E. Perilla, Antec. Conf. Proc. 73 (2015), 148-152.
[34] B.J. Lee, S. Roy, S.C. Jana, Antec. Conf. Proc. 67 (2009), 126-130.
[35] S. Roy, B.J. Lee, Z.M. Kakish, S.C. Jana, Macromolecules (2012) 45.
[36+ M. Szołyga, M. Dutkiewicz, B. Marciniec, H. Maciejewski, Polimery 58 (2013) 766.
[37] C.-S. Kim, H.-D. Jeong, J. Phy. Chem. B 112 (2008), 51, 16257-16260.
[38] X. Wang, L. Wu, J. Li, J. Therm. Anal. Calorim. 109 (2012), 323–329.
[39] X. Wang, J. Li, L. Wua, Polym. Adv. Technol. 22 (2011), 2151–2156.
[40] M.L. Di Lorenzo, M. Frigione, J. Polym. Eng. 17 (1997) 429.
[41] Z. Horvath, B. Gyarmati, A. Menyhard, P. Doshev, M. Gahleitner, J. Varga, B. Pukanszky, RSC
Adv. 17 (2014) 429.
[42] M. Kristiansen, T. Tervoort, P. Smith, H. Goossens, Macromolecules 38 (2005) 25.
[43] M. Thomas, PhD thesis (1985).
[44] Norm, Plastics—Determination of Tensile Properties—Part 1: General Principles; ISO 527–
1:2012; 2012.
[45] M.L. Di Lorenzo, S. Cimmino, C.J. Silvestre, J. Appl. Polym. Sci. 82 (2001) 358.
[46] S. Vyazovkin, K. Chrissafis, M.L. Di Lorenzo, N. Koga, M. Pijolat, B. Roduit, N. Sbirrazzuoli, J.J.
Sunol, Thermochim. Acta 590 (2014) 1.
[47] M. L. Di Lorenzo, Polymer 42 (2001) 9441.
[48] M.R. Nobile, L. Bove, E. Somma, I. Kruszelnicka, T. Sterzynski, Polym. Eng. Sci. 45 (2005) 2.
[49] M. Barczewski, D. Matykiewicz, J. Andrzejewski, Macromol. Res. 23 (2015) 9.
[50] B. Strzemiecka, B. Borek, A. Voelkel, J. Adhes. Sci. Technol. 30 (2016) 1.
[51] C. Wan, F. Zhao, X. Bao, B. Kandasubramanian, M. Duggan, J. Polym. Sci. B Polym. Phys. 47
(2009) 121.
[52] M.S. Sevegney, R.M. Kannan, A.R. Siedle, A. Percha, J. Polym. Sci. B Polym. Phys. 43 (2005)
439.
[53] T. Sterzyoski, M. Lambla, F. Georgi, M. Thomas, Int. Polym. Proc. 12 (1997) 1.
[54] Norm Tworzywa sztuczne - Oznaczanie współczynnika przepuszczania światła i zamglenia; PN-
84/C-89100; 1984.
[55] W. Brostow, H.E. Hagg Lobland, M. Narkis, J. Mater. Res. 21 (2006) 2422.
43
Literature 44
[56] W. Brostow, H.E. Hagg Lobland, S. Khoja, Mater. Lett. 159 (2015) 478.
[57] P. J. Launer, B. Arkles, Reprinted from Silicon Compounds: Silanes & Silicones, Gelest, Inc
Morrisville, PA.
[58] I. P. Lisovsky, V. G. Lytovchenko, D. O. Mazunov, A. Szekeres, Ukr. J. Phys. 50 (2005) 78.
[59] S. Inagaki, Y. Fukushima, K. Kuroda, J. Chem. Soc. Chem. Commun. 8 (1993) 680.
[60] B. Wunderlich, Thermal Analysis, Academic Press, New York, 1990.
[61] L. C. Lopez, G. L. Wilkens, Polymer 30 (1989) 882.
[62] B. Fillon, A. Thierry, B. Lotz, J.C. Wittmann, J. Therm.Anal. 42 (1994) 721.
[63] L. Balzano, S. Rastogi, W. Gerrit, M. Peters, Macromolecules 41 (2008) 399.
[64+ A. Menyhárd, M. Gahleitner, J. Varga, K. Bernreitner, P. Jääskeläinen, H. Oysaed, B.
Pukánszky, Eur. Polym J. 45 (2009) 11.
[65] B. Monasse, J.M. Haudin, Colloid Polym. Sci. 263 (1985) 822.
[66] M. L. Di Lorenzo, S. Cimmino, C. Silvestre, Macromolecules 33 (2000) 3828.
[67] A. Thierry, B. Fillon, C. Straupe, B. Lotz, J.C. Wittmann, Prog. Colloid Polym. Sci. (1992) 87.
[68] B. Strzemiecka, A. Voelkel, M. Hinz, M. Rogozik, J. Chromatogr. A (2014) 1368.
[69+ I. Poljanšek, M. Krajnc, Acta Chim. Slov. (2005) 52.
[70] F.M. Willmouth, Transparency, Translucency and Gloss, Elsevier, London–New York, 1986.
Chap. 5.
[71] J.M. Haudin, Optical Studies of Polymer Morphology, Elsevier, Barking, 1986, p. 167.
[72] Z. Horvath, A. Menyhard, P. Doshev, M. Gahleiner, G. Voros, J. Varga, B. Pukanszky, ACS Appl.
Mater. Inter. 6 (2014) 7456.
[73] T.A. Shepard, C.R. Delsorbo, R.M. Louth, J.L. Walborn, D.A. Norman, N.G. Harvey, R.J.
Spontak, J. Polym. Sci. Part B: Polym. Phys. 35 (1997) 2617.
[75] X. Zhang, F. Xie, Z. Pen, Y. Zhang, Y. Zhang, W. Zhou, Eur. Polym. J. 38 (2002) 1.
[76] H. Bai, Y. Wang, B. Song, L. Han, J. Appl. Polym. Sci. 108 (2008) 3270.
[77+ M. Aboulfaraj, C. G’sell, B. Ulrich, A. Dahoun, Polymer 36 (1995) 4.
[78] E. A. Wilder, R. J. Spontak, C. K. Hall, Mol. Phys. 101 (2003) 3017.
[79] Official website of Sigma Aldrich www.sigmaaldrich.com (accessed on March 31, 2017).
[80] E. Manias, A. Touny, L. Wu, K. Strawhecker, B. Lu, T.C. Chung, Chem. Mat. 13 (2001) 10.
[81] M. Sumita, K. Sakata, S. Asai, K. Miyasaka, H. Nakagawa, Polym. Bull. 25 (1991) 265-271.
[82] W.C.J. Zuiderduin, C. Westzaan, J. Huétink, R.J. Gaymans, Polymer 44 (2002) 261-275.
[83] M. Barczewski, D. Matykiewicz, J. Andrzejewski, K. Skórczewska, J. Adv. Res. 7 (2016) 3, 373-
380.
[84] M. Barczewski, D. Czarnecka-Komorowska, J. Andrzejewski, T. Sterzyoski, M. Dutkiewicz, B.
Dudziec, Polymers 58 (2013) 10, 805-815.
[85] D. Paukszta, M. Szostak, M. Rogacz, Polymers 59 (2014) 2, 165-169.
[86] K. Bula, M. Knitter, Drewno 59 (2016) 197, 205-211.
[87] M. Kazayawoko, J.J. Mbalatinecz, L.M. Matuana, J. Mat. Sci. 34 (1999), 24, 6189-6199.
[88] N.F. Zaaba, H. Ismail, M. Jaafar, Bioresources 9 (2014), 2, 2128-2142.
[89] M. Zahedi, H. Pirayesh, H. Khanjanzadeh, M. M. Tabar, Mater. Des. 51 (2013) 803-809.
[90] G. W. Beckermann, K.L. Pickering, Composites Part A 39 (2008) 979-988.
*91+ M. Dobrzyoska-Mizera, T. Sterzyoski, M. L. Di Lorenzo, PL patent application no. P.421623,
May 18, 2017.
44
45
Attachment 1
M. Dobrzyoska-Mizera, M. Dutkiewicz, T. Sterzyoski, M. L. Di Lorenzo, Isotactic

polypropylene modified with sorbitol-based derivative and siloxane-silsesquioxane resin,
European Polymer Journal 2016, 85, 62-71.
45
46
Attachment 2
M. Dobrzyoska-Mizera, M. Dutkiewicz, T. Sterzyoski, M. L. Di Lorenzo, Polypropylene-

based composites containing sorbitol-based nucleating agent and siloxane-silsesquioxane
resin, Journal of Applied Polymer Science 2016, 133, 22.
46
47
Attachment 3
M. Dobrzyoska-Mizera, M. Dutkiewicz, T. Sterzyoski, M. L. Di Lorenzo, Interfacial

enhancement of polypropylene composites modified with sorbitol derivatives and
siloxane-silsesquioxane resin, AIP Conference Proceedings 2015, 1695, 020049.
47
48
Attachment 4
M. Dobrzyoska-Mizera, T. Sterzyoski, M. L. Di Lorenzo, Kompozyt izotaktycznego

polipropylenu o kontrolowanej szybkości krystalizacji i polepszonych właściwościach
optycznych oraz sposób jego otrzymywania, patent no. P.421623.
48
49
Attachment 5
M. Barczewski, M. Dobrzyoska-Mizera, B. Dudziec, T. Sterzyoski, Influence of a sorbitol-

based nucleating agent modified with silsesquioxanes on the non-isothermal
crystallization of isotactic polypropylene, Journal of Applied Polymer Science 2014, 131, 8.
49
50
Attachment 6
M. Barczewski, D. Chmielewska, M. Dobrzyoska-Mizera, B. Dudziec, T. Sterzyoski,

Thermal stability and flammability of polypropylene-silsesquioxane nanocomposites,
International Journal of Polymer Analysis and Characterization 2014, 6, 19.
50
51
Attachment 7
M. Barczewski, B. Dudziec, M. Dobrzyoska-Mizera, T. Sterzyoski, Synthesis and influence

of sodium benzoate silsesquioxane based nucleating agent on thermal and mechanical
properties of isotactic polypropylene, Journal of Macromolecular Science, Part A: Pure and
Applied Chemistry 2014, 11, 51.
51
52
Attachment 8
M. Barczewski, M. Dobrzyoska-Mizera, J. Andrzejewski, D. Chmielewska, Ocena

właściwości włókien orientowanych wykonanych z nukleowanego izotaktycznego
polipropylenu modyfikowanego silseskwioksanami, Przetwórstwo Tworzyw 2013, 3, 153.
52
53
Attachment 9
M. Dobrzyoska-Mizera, M. Barczewski, B. Dudziec, T. Sterzyoski, Influence of the cooling

rate on the non-isothermal crystallization of iPP nucleated with DMDBS and
silsesquioxanes, Polimery 2013, 11/12, 58.
53

Monika Dobrzynska-Mizera Structure and Properties of Isotactic Polypropylene Modified With Siloxane-Silsesquioxane Resin and Sorbitol...

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Monika Dobrzynska-Mizera Structure and Properties of Isotactic Polypropylene Modified With Siloxane-Silsesquioxane Resin and Sorbitol...

Uploaded by

Copyright:

Available Formats

POZNAN UNIVERSITY OF TECHNOLOGY

INSTITUTE OF MATERIALS TECHNOLOGY

Structure and properties of isotactic polypropylene

The presented dissertation is a guide throughout monothematic series of

POZNAO, JUNE 2017

I am forever indebted to my academic supervisors, Prof. Tomasz Sterzyoski and

I would like to thank my beloved husband Marcin for his unremitting

I am grateful to my parents for everything. You made me into who I am.

Izotaktyczny polipropylen (iPP) jest semikrystalicznym i polimorficznym polimerem

mają możliwośd formowania złożonych adduktów poprzez wiązania wodorowe. Formowanie

opakowaniowe. Ponadto, wykonano badania statycznej próby rozciągania z wykorzystaniem

The presented research was conducted at Poznan University of Technology, Institute of

Series of scientific publications

1. M. Dobrzyoska-Mizera, M. Dutkiewicz, T. Sterzyoski, M. L. Di Lorenzo, Isotactic

1. Kompozyty na bazie polipropylenu modyfikowane pochodną sorbitolu i żywicą

DSC Differential Scanning Calorimetry

FTIR Fourier Transform Infrared Spectroscopy

iPP Isotactic polypropylene

MAPP polypropylene-graft-maleic anhydride

NX8000 1,2,3-tridesoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol sorbitol

POM Polarized Optical Microscopy

SiOPh Siloxane-silsesquioxane resin modified with phenyl groups

SEM Scanning Electron Microscopy

WAXD Wide-Angle X-Ray Diffraction

Fig. 2.1 Chemical structures of (a) DMDBS, (b) NX8000

2.2 Preparation of SiOPh

The synthesis was conducted using two-step acid-base co-condensation of

Fig. 2.2 Chemical structure of SiOPh

2.3 Sample preparation

Table 2.1 Designations and mass concentrations of samples

iPP DMDBS SiOPh iPP NX8000 SiOPh

The composites were compression-molded with a Collin Hydraulic Laboratory Forming

2.4.1 Scanning Electron Microscopy (SEM)

2.4.2 Differential Scanning Calorimetry (DSC)

2.4.3 Polarized Optical Microscopy (POM)

2.4.4 Oscillatory Rheological Measurements

2.4.5 Fourier Transform Infrared Spectroscopy (FTIR)

2.4.6 Wide-Angle X-ray Diffraction (WAXD)

2.4.8 Static Tensile Tests

3. Results and discussion

3.1 Structure and crystallization behavior

Structure and morphology of the novel phenyl siloxane-silsesquioxane resin, synthesized

Fig. 3.1 SEM micrograph showing morphology of SiOPh particles

Fig. 3.2 FTIR spectrum of SiOPh resin

Calorimetric studies were realized by differential scanning calorimetry measurements at

Addition of the siloxane-silsesquioxane resin to iPP/DMDBS formulation slightly reduces

SiOPh, as seen in Figure 3.5-a. The influence of SiOPh/DMDBS composition on nucleation

Cooling rate [C/min] Cooling rate [C/min]

Cooling rate [C/min] Cooling rate [C/min]

3.2 Rheological properties

Differential scanning calorimetry data provided information on crystallization upon

3.3 Intermolecular interactions

3.4 Crystal phases in polypropylene

Wide-angle X-ray diffraction (WAXD) analyses were performed particularly to determine

3.5 Performance of iPP-based composites

Mechanical properties of the iPP/DMDBS/SiOPh composites were determined using static

Mechanical properties of the iPP/NX8000/SiOPh composites are summarized in Figure

The mechanical properties of semicrystalline polymer composites depend markedly on

3.6 Interfacial enhancement of iPP-based composites

Fig. 3.16. Chemical structure of polypropylene-graft-maleic anhydride (MAPP) [79]

Table 3.3 Designations and mass concentrations of compatibilized samples

Mass concentration [%]