dimanche 23 août 2026

DUAL-PHASE RHEOLOGY PROTOCOL (DPRP)



Re-Formulation of the Rheological Equations of Polymer Melts Pursuant to the Dual-Phase and Cross-Dual-Phase Model of Dissipative Interactions.

 Description of the Dual-Phase Rheology Protocol (DPRP). 



This graph compares the shear-thinning rheological curves for the data (black line), for Dual-Phase 1 (DP1), Dual-Phase 2 (DP2), their sum (DP1+DP2), and their sum with the addition of the inactive Dual-Phase portion of the network of interacting Dual-conformers: (DP1+DP2+dc), the green triangles pointing down. The viscosity of each Dual-Phase is calculated from its c structure, c = c1+c2, with c = (G’/G”)2 ; c1 and c2 are the respective contributions of the free volume and of the rotation isomeric state (RIS) of the Dual-conformers to the active elasticity c.


ABSTRACT

 

The current equations describing the dynamic rheology of polymer melts provide the correlations between the modulus of visco-elasticity, G*(w), splitting into its elastic and viscous moduli, G’(w) and G”(w), respectively, and the frequency of the shear deformation applied to the melt, w. The dynamic viscosity of the melt, h* = G*/w is usually used to compare melts of different chemical nature or to study the effect of molecular weight, M, its dispersity, and the presence or the absence of branches, short or long. The equations also describe the influence of external variables on the rheological state of the melt: temperature and pressure. The terms and constants that enter the equations of rheology have themselves been interpreted, to a large extent, by molecular mechanisms triggered by the changes occurring to the statistical description of the individual chains: the dynamic molecular models of Rouse (for un-entangled melts) and of de Gennes (reptation) for entangled melts illustrate the current formulation and understanding of the rheology of polymer melts. On the other hand, we have pointed out in several publications the problems surfacing in the classical molecular interpretation of the rheological data when revisited by our analysis, and the contradictions arising from these models when they are applied to theunderstanding of new experimental work on“the strain-induced time dependence of the melt viscosity” leading to the technologies of “Rheo-Fluidification” of melts and of their “sustained-Orientation”. In short, we have concluded that the current comprehension of the visco-elasticity of polymers, in particular of the entanglement concept,is not compatible with the reality of new experimental facts and, therefore, that the current accepted theories should be debated and revised; more generally, that a different approach to the physics of interactions in polymers should be considered. We have already introduced the principles of such a theory of interactions of Dual-conformers in which the statistical system is no longer a single macromolecule, but a self-generated collective network of Dual-Conformers belongingto the macromolecules. The local deformation of the Dual-conformers and the collective network enthalpy and entropy are interactively emerging from the solution of the Grain-Field Statistics applied to the interactions between the Dual-conformers, demonstrating the dissipative character of the solutions: this is our new foundation to explain the observed experimental facts, old and new, regarding the visco-elastic effects of melts under shear-deformation, linear or non-linear. This paper presents the Dual-Phase Rheology Protocol (DPRP) i.e. how to derive the parameters of the new statistical approach from the visco-elastic moduli G’(w,T) and G”(w,T) in dynamic rheology. In particular, it is shown that a completely different empirical presentation of the rheological results can be expressed in terms revealingthe relevance of the Dual-Phase and Cross-Dual-Phase concepts. We introduce, for the 1st time, an empirical analysis of the data that permits to relate the rheological properties of an entangled melt (M > Mc, the entanglement molecular weight) to the stability of the solution presented by the split of Dual-Phases into Cross-Dual-Phases. In other words, the “entanglement” of the macromolecules can be quantified in terms of the viscosity, h,  and the intrinsic elasticity, c=(G’/G*)2 of the individual interactive Dual-Phases emerging from the split to re-establish a new rheological stability of the melt as M increases. This paper also introduces a roaster of new rheological markers that can be traced to analyze phenomena visible in rheology, widening the panel of analytical tools available to characterize difficult situations (blends, branches etc.).

 

Keywords

 

Dual-Phase Rheology Protocol, DPRP, Dual-Phase model, Cross-Dual-Phase model, Grain-Field-Statistics, Dual Conformer, Cross-Duality, Entanglement, Disentanglement, Rheo-Fluidification, Sustained-Orientation, entanglement instability, polymer melt rheology, molecular dynamics, reptation, Newtonian viscosity, Maxwell’s rheology equations, Thermo-Vogel-Fulcher equation of viscosity, MX-PLOT, interactive coupling, TLL transition.

 

 

 

TABLE OF CONTENT

ABSRACT  

TABLE OF CONTENT

INTRODUCTION  p.4

GLOSSARY OF THE TERMS AND BACKGROUND DEFINITIONS. p.6

          1. Dual-Splitting. p.6

          2. Scaling of the Dual-Split Terms. Scales Correlation Maps. p.7

            3. The Dynamic Thermo-Vogel-Fulcher Equation (DTVF). p.8

            4.  MX-PLOTS. p.10

           5.  Visco-Elastic Range Dynamic Fragmentation. p.11

          6. Classical Entanglement Rheological Criteria.  Dual-Phase Rheological   Proto  col (DPRP): Single-Dual-Phase vs. Two Dual-Phases Criteria. p.12

          7. Dual-Phase Dynamic Frequencies. p.13

 

ILLUSTRATION OF THE DPRP DEFINITIONS AND PARAMETERS. p.14

 

          8. Data Assessment. p.14

          9. The TVF equation. p.20

          10. The MX-PLOT.p.20

          11. The Structure of c into c1 and c2 . p.30

          12. Discontinuities. Asymmetrical roles of c1 and c2. p.39

 

SCALING OF THE DUAL-PHASE TERMS.  p.48

 

          13. Equations for the structure of c by splitting c vs G* using Eq. 2.  p.48

          14. Analysis of the X-scale and Y-scale. p.50

          15. Traditional Analysis of the X-scale and Y-scale. p.50

          16. Scale Correlations Maps: The “Esoteric” Approach. p.60

          17. Single Dual-Phase (DP) or Cross (Entangled) Dual-Phases (DP1, DP2).            p.70

          18. Construction of the Cross-Dual-Phases: the Linear approach. p.73

          19. Correlations between the Active terms of the Structure of c1(w)  and c2(w):   B1, B2, R1                      and R2.  Expression of the Cross-Duality. p.83

 

          20. Construction of the Cross-Dual-Phases: The Non-Linear Approach. p.92

          21. Conversion of the c structure results to Viscosity. p.100

          22. The Question of the “dc” terms (Fig.11i). p.106

          23. Dynamic Network Frequencies. p.107

          24. Strain Induced Time dependence of viscoelasticity. p.110

         25. Orientation of the Network of Dissipative Interactions. p.115

 

SUMMARY OF THE DUAL-PHASE RHEOLOGICAL PROTOCOL (DPRP). p.117

 

DISCUSSION. p.121

 

CONCLUSIONS p.132

 

ACKNOWLEDGMENTS. p.134

 

REFERENCES. p.135

 

 

EXCERPT from the DPRP paper:

 

“We have accumulated empirical knowledge through experimentation [1, 3-5] that enables the determination of the dynamic parameters (w, strain) that trigger the time dependence of the rheological parameters in polymer melts; in other words, we know empirically how to generate the rheological evidence that is denied by the current paradigm of rheology [6-8], but we had not been able to predict it mathematically until now. Our challenging model of entanglements as Cross-Dual-Phases can now address mathematically the time dependence of the rheological state under specific non-linear rheological conditions [1,38,43]; it can also explain the difference between “Rheo-Fluidification” and “Sustained-Orientation”, in particular why it was more difficult, retrospectively, to obtain the “Sustained-Orientation” benefits than the Rheo-Fluidification ones”.

 

FULL PAPER (downloadable):

https://doi.org/10.5281/zenodo.20645765

 

 

 

 

Jean Pierre Ibar

jpibar@alum.mit.edu



lundi 14 avril 2025

........................THE SHADOW OF TIME........................ Interview with Professor Apixi Crapinovitch

 

The Shadow of Time

Interview with Professor Apixi Crapinovitch*

 


Portrait of Prof. A. Crapinovitch

 

 

J.P. IBAR (JPI): Why the “Shadow of Time”: what does it mean?

 

Prof. A. CRAPINOVITCH (PAC): It is a metaphor to indicate that Time can be considered a “substance” with a variety of structures. Only substances give rise to shadows when light shines upon them, hence the metaphor.

 

JPI: It is unusual and intriguing to say that Time is a substance! Can you summarize in a few words what kind of substance we are talking about?

 

PAC: Our view is that Time exists and its structures can be described mathematically like it is done for atoms or cells. Time is made up of “grains”, the grains of time that we call “chronons”, that can perpetually generate and couple interactively in open dissipative systems that structure internally (verticality of Time) and externally (horizontality of Time).

 

JPI: Who is “we”? I know you were introduced at the Pioche Conference   on December 12th, yet could you briefly introduce yourself for this interview.

 

PAC: I am a 12th generation humanoid robot from the star system Kepler-452 (b planet) in the Constellation Cygnus sent to earth to share our understanding of the Universe.  CRAP” refers to: “our knowledge is questionable”, “NOVITCH” means “new” or “the edge”in our AI language. My function is to share RESEARCH AT THE EDGE of our understanding, work in progress (WIP) in other words.

 

JPI: Would you then say that, in your star system, knowledge is better described by “crap in progress” ?

 

PAC: Exactly!

 

JPI  You told us of your in depth familiarity with our scientific understanding of the Universe here on earth; actually you summarized at the conference your interpretation(s) of  relativity, quantum mechanics, dark matter, black holes etc., and declared, tell me if I am wrong: “these extraordinary achievements lack a basic fundamental ingredient: the understanding of Time”. And, according to you, the variable “time” has been mathematically mishandled, abusively considered to behave at our disposal: as an homogeneous scalar that can be reduced to infinitely small values to solve differential equations, the holy grail of mathematical physics, or as periodic functions in wave functions to describe propagation in space of quanta of energy, the electromagnetic wave/photons. For instance, you explained that understanding Time “inside the atom” versus “outside the atom is key to establish the compatibility between relativity and quantum theory...

 

PAC. It is true that the variable time remains essentially a “variable of convenience” in the development of relativity and quantum mechanics: it is not needed in the formulation of the Schrödinger equation, and, in relativity, it is “elastically” bounded to space to define spacetime, a limitation that we consider a mistake.

 

JPI: What do you mean by “elastically”? Are you referring to the fourth dimension “ct” in the Pythagorean calculation of distance between two points in spacetime (where “c” is the velocity of electromagnetic waves in vacuum)?

 

PAC: Yes that term generates a duality between time and space, which was a fantastic idea by Einstein, but this link is “elastic” (reversible and in phase) and not “dissipative”, meaning it is not rate dependent nor temperature dependent, the two drives of dissipation. Hence, the whole relativity must be reconsidered!. We know your work rewriting the paradigm for the viscoelastic behavior of macromolecular materials from dissipative statistical systems: the relaxation times are slow for these long chains which permits to study transients, not simply steady states, a great advantage to discover all the fundamental parameters of an event, but not just that,  these materials show that the elastic and dissipative components of stress and strain are not in phase and depend on temperature and on the strain rate. If the strain rate is increased to very fast values, a melt or a rubber behaves like a glass, i.e. like an elastic solid, but this elastic behavior is only a special case of a more general viscoelastic solution. By analogy, the link between time and space should be reworked to be more general than limited to the special case of an elastic link. Remember that the velocity of light can be lowered when the medium that it goes through is not the vacuum and it also becomes temperature dependent. These are not taken into account in classical relativity.

 

JPI: Are you saying that Time could be a complex vector instead of a scalar and include both an elastic and a dissipative component?

 

PAC: Sort of! This could be a metaphor for the real structure of Time, which is in fact more complex as I suggested during the Pioche conference: the structure of Time is the result of two compensating mechanisms of structuration, one vertical that involves the periodic nature of time over several “scales” working in harmony (the scales are “entangled” down to the Planck level), and one horizontal that controls the open aspect of the dynamics by generating new chronons as needed.

 

JPI:  Where does Space play a role, how does it interact with Time?

 

PAC: Space interacts with Time to permit differentiating the “conformation type” of the chronon: the “elongated” conformations and the “flexed” conformations, and to control the rate of generation of new chronons. The horizontal mechanism (“cloning”) controls the quantity of chronons needed to achieve an event in time-space, the vertical mechanism (“folding”) controls their scale and the type of conformation of the chronons needed at that scale. The compensation between the horizontal and the vertical mechanism is subject to dissipative effects: heat is produced or removed from the vertical axis, affecting the kinetics on both axes, and photons are generated as another dissipative solution to control the internal energy of the open system. These are the basic mechanisms requiring the cooperation of Time and Space at all scales to allow any event to evolve dynamically.

 

JPI: In that scenario, is Time “ahead of Space”, so to speak, or are they the dual faces of the same coin? In other words is Time “God” and “Space” his son, if you know what I refer to, or are they twins? By the way, how do you call the theoretical model that you describe?

 

PAC: I recognize the religion you are referring to, actually the analogy gets even deeper since we have Time, Space and Matter, a trilogy because of the dissipative effect (I will discuss this later). The dissipative energy generates the stability of certain solutions which results in the distinction between PAST and PRESENT and their interaction generates new solutions (hence the FUTURE). This process depends on the type of event considered and is therefore different at different places where events take place: this means that neither space nor Time is homogeneous. Regions of space have different time clocks if you want, this is what we mean by the inhomogeneity of the structures of time. Of course, the drastic consequence of this is that different regions of space do not share a common time line and it is wrong to try to cross these inhomogeneous time zones to extrapolate what the past looked like, as your modern astrophysicists on earth persist doing. This lack of understanding of Time results in the incoherencies observed by the James Webb telescope and the current challenges to the standard big-Bang cosmological model. Our open dissipative model of Time raises new questions (crap in progress…):

 

- Is a black hole the illustration of the vertical mechanism in action  without horizontality, with no emission of photons?

- Does the compensation between the horizontal and the vertical axes of Time explain THE FLOW OF TIME and THE EXPANSION OF SPACE (with its current controversial dark energy explanation)?  Simply put, events generate additional chronons in open dissipative systems, so time is expanded and so is space. In other words, the Flow of Time and the Space expansion of the Universe are the same phenomena, hence the dark energy issue dissolves away!

 

By the way, the theoretical model is called The Energetic Kinetic Network (EKNET) of Open Dissipative Interactions (EKNET-ODI), often abstracted EKNET. My lab in planet Kepler-452b is named EKNET RESEARCH CAMPUS in memory of your own research on earth.

 

JPI: Well, I am not dead yet, as you can see  by yourself!...As you just mentioned, you have not talked about MATTER in this interview and I remember that in your conference at Pioche you had dualities and Cross-dualities: SPACE TIME and MATTER for instance. Where is the reality of Matter coming from?

 

PAC: Matter is a past stable solution resulting from the weaving of Space and Time. The coupling of space and time occurs everywhere all the time: it has been repeated hundreds of billion trillion times per second generating a super giant network of trial-events. The trial-events are described by the Grain-Field-Statistics of Dissipative Interactions which we have borrowed from your own work in polymer physics. I guess this is why you have invited me for the conference at Pioche and for this interview. You have taught us the duality of the conformers in polymer systems to be of the F-type or b-type based on the ability of the local interactive field to create b-grains that are distinct from their surrounding, the F-dual conformers; the b-grains are nanometric agglomerations of b-conformers regardless of their spatial conformation (cis, gauche or trans). These nodular agglomerates are localizable in space when the dissipative energy of the system remains above 0, which occurs below a certain temperature TLL for polymers. In any case, it means that temperature is involved in the process of dissipation and thus of the stabilization of coupling space and time to generate “Matter”. To make a long story short, the application of your statistical dissipative network to a set of chronons having various conformations (needing different space volumes to manifest their differences) results in an inhomogeneity of the spacetime density (another difference with the Einstein’s hypothesis of homogeneity of spacetime) and the possibility to obtain stable states which, in the standard model, represent the metaphors of the “elementary particles”. Your Grain-Field-Statistics also generates entangled states by splitting systems (“folding”) which become unstable when the size of their agglomerates saturates the dissipative energy. This description of “entanglement states” when the dissipative energy of the single system’s state becomes too large can be transposed to structure the vertically of the interactions of a set of chronons. A stable state (a “particle”) is the compensation point of the interactions  at a certain scale. A complex particle (such as an atom) is a superposition of more than one scale via a process of “entanglement”. For instance an atom has two scales, one scale for its “nucleus” and one scale for its “electrons” (here I am purposely using the earth’s particle definition of our stable states). There is an horizontal structure associated with each scale, yet the cross-duality of the atom is due to the entanglement between the scales. The entanglement between the scales and the structure for each scale is the realm of “fragmentation”, where discontinuities in the mathematical descriptions are the norm, a situation which your physicists have called “quantum mechanics”. The  fragmentation of the structure of time in discrete blocks is the way dissipative systems of interaction decay mathematically and, perhaps, those discrete blocks are the equivalent of the “quanta” of energy in the Standard model, although the exact correspondence may (or may not) need to be established.

 

JPI:  Does the presence of Matter, which you describe as stable past solutions, influence the mechanism of new events, let’s call them occurring in the present?

 

PAC: Absolutely! We are talking about a weaved structure, a network of interactions with a past. Gravity is really the result of past structures interfering with the present dynamism of their stability in the growing network. All the past structures are weaved by the same mechanisms of interactions between time and space, repeated many times, but not necessarily at the same stage of evolution.

 

JPI: Do you mean that Gravity is embedded in the coupling between TIME, SPACE and MATTER, explained by the history of the network of interactions? Are you asserting that Gravity is actually unified with the other types of interactions?

 

PAC: Yes, of course, all the types of interactions of earth’s Physics (strong forces, weak forces, electromagnetic and gravity forces) are separate features of the same build up of the EKNET-ODI. There is one single such network for a given Universe, yours and mine are parts of the same: we share the same mechanisms of interactions and are interdependent by our common origin, only separated by1400 light years pursuant to your own earth’s calculations. Yet, probably, several truly independent such networks at different stages of evolution exist, with  no interactions between them, no possibility to share any information and we will never know how many of those Universes exist, let alone if they do exist!

 

JPI: Can we now turn to the topics of “units” in physics and the existence of “fundamental constants” for which you claimed during your conference at Pioche that they were the earth’s “weak concepts” to understand the fundamental mechanisms of the formation of the interactions in the Universe; you actually said “the Universes” and I thank you for your explanation above to enlighten this Multi-Universes possibility.

 

PAC: In your physics on earth, you have several units defined to characterize events’ evolution by numbers, and this is a clever practical way to normalize the changes and to name what the changes apply to. For instance, the normalization for Time is the “second”, for space the “meter”, for the quantity of matter the “gram” etc. And then, you have the fundamental constants: the Avogadro number, the Boltzmann’s number, the velocity of light, the Planck constant, so on and so forth, in total 26 fundamental constants to describe the “standard model of physics’. These fundamental constants are obtained by experimentation, they are the links between the models and the reality, you cannot explain their value. The weakness of this approach is that these fundamental constants are “fitting constants”, they are only fundamental with respect to the model of nature assumed to prevail. Our model is the description of a process of generation of Time, Space and Matter, a mechanism of interactions between these 3 elements that repeats itself like Russian  dolls unfolding. We claim in our approach that we only need 3 units, time, space and energy, and 3 fundamental values should be enough to describe the 1st step of the genesis of the Dissipative Network; all the other steps (by folding and cloning) are auto-generated by the assumptions regarding the compensations between the horizontal and vertical axes, defining the scale, the b and F conformational states of the chronons and the requirement to optimize the dissipative energy either locally or collectively. In other words, all the other constants should derive from the fundamental ones, one way or the other. The response to the question “do we fundamentally need all these units and constants” is: YES,  the Standard model of Physics needs 26 fundamental constants to describe the interactions between the particles of the model (12 fundamental fermions and 5 fundamental bosons) that assemble and combine to generate 61 particles that render possible the events occurring in the Universe, and NO, it is not yet possible to ascertain that the EKNET of Open dissipative Interactions can be generated with only 3 constants to account for all the events occurring in the Universe. Yet the current cosmological model and the standard model of particles face so many  challenges that the proposal of a new paradigm to avoid their multiple contradictions seems inevitable: the incompatibility between general relativity and quantum mechanics predictions, the dark matter mystery, the dark energy mystery, the incompatibility between gravity and the other 3 forces of nature etc. have been discussed for ages with no real consensus ahead. Is it not time to understand TIME differently? 

 

JPI:  So much to do still…Thank you Professor CRAPINOVITCH for exposing these new possible interpretations of how TIME works to weave the microscopic to the macroscopic. At least some Buddhists will clearly endorse your propositions! Catholics might enjoy your Trinity metaphor but not your collapse of the Big Bang explanation of the 6 first days of creation... As for Physicists, you know how the Thomas Kuhn’s paradigm evolution works...

 

PAC: “TIME IS IN THE WORKS” was the title of my talk at Pioche Projects. We are still in the shadow of TIME,  but CRAP IS IN PROGRESS, for sure! Thank you for inviting me.

Link to Prof. A. Crapinovitch EKNET  RESEARCH CAMPUS classes: 

Prof. A. Crapinovitch EKNET CAMPUS Kepler-52b

 


 

 

This blog post is dedicated to Django Ibar on his birthday 4/11/2025

mercredi 1 mars 2023

THE DECEPTION TEMPTATION

THE DECEPTION TEMPTATION

The End of Scientific Enlightenment ?

 


The notion of ‘good and bad’ was part of a moral code inspired by the 10 commandments of the Bible, for instance: you shall not lie was one of them, and since you would constantly be tempted to lie anyway (to take advantage of others or brag about yourself etc.) you were told to learn how to control the temptation to lie. The temptation was driven by the Devil himself, whispering in your ears: do it..., no one will ever know…, it’s gonna be all right! But every Sunday God himself would step down to sermon that you had the choice to be a good person and say NO to the deception temptation.

 

WHY SHOULD YOU? whispered the Devil.

 

And then came the learning of science principles, the QED SCIENTIFIC PROOF, more powerful than the 10 commandments: you don’t need to lie to convince, you just need to prove it. This was demonstrated by Descartes and Newton and became the Age of Enlightenment, then by Einstein and Feynman and millions of others to become the era of REASON.

 

REALLY... REALLY? whispered the Devil who hastily prepared new tools to mess around all this good will.

 

Fast forward to the TRUMP and POUTIN century with its panoply of fine tuned instruments of deception: Mirrors, Illusions, Video fake montages, Propaganda, Disinformation, Fake News, Deep Fakes, Self-paid Publications etc., with as primary result the disorientation in people’s mind:  who tells the TRUTH?

 

All these deception tools were rapidly endorsed and mastered by the industry and by the governments, legitimized under the disguise of sales promotion information, publicity, marketing, information mixed with entertainment etc.

 

Disinformation practices have nowadays infiltrated all aspects of our life, even the Justice system that has finally surrendered to the practice of overpaid lawyers helping their clients lie under oath. No wonder the Courts have become the playground of the rich and famous at the expense of Justice for all!

 

THANK YOU… whispered the Devil!...GLAD TO BE OF SERVICE!

 

Someone argues back:

 

But deception is not in sciencescientistsyou knowthose are the incorruptible pillars of the search for the TRUTH!.

 

OH YEH?… jubilated the Devil…CHECK MY LATEST ACHIEVEMENT BELOW:

 

I have suggested for the last decade to the polymer scientific community to abandon the current paradigm of polymer physics that is used to describe the molecular dynamics of macromolecules. Essentially, this paradigm consists of two models: the Rouse model and the reptation model. There are, of course, ramifications and improvements that have been applied to modify these models. Yet, I have exposed the problems and deficiencies of the current paradigm to explain old and new experimental evidence that have been validated by other independent researchers, in particular the “sustained orientation” property of Rheo-Fluidified melts that totally contradicts the current molecular dynamics paradigm [1].

 

The fundamental question that I address in my books [1-5] relates to the statistical treatment of the interactions between macromolecules that should be applied to polymers: whether the classic Boltzmann’s statistics of systems made up of macromolecules should be used (this solution is the classical approach that led to the current paradigm), or another statistical model and another statistical system should be considered?

 

 I define and explore in my research the use of a dissipative statistical description of the interactions, the Grain-Field Statistics, to quantitatively describe the viscoelastic behavior of polymers. This is the objective of the new paradigm taught and disseminated by the New School Polymer Physics [1-5].

 

In his famous book “The Structure of Scientific Revolutions” [6], Thomas Kuhn identified the 3 criteria that define the strategy of current paradigm’s gate keepers to oppose the dissemination of a new paradigm challenging their established one:

 

 

              “- 1 rejection by impossibility to leave behind the previous paradigm,

                - 2 accept the disruptive necessity for a change but find it very hard to adapt to                                         the new paradigm.

                - 3 attempt to sabotage by deception the new paradigm to prevent its                                             dissemination”

 

Amazingly, the review process of my 1st book [1] led to confirm these 3 statements “by the book”.

 

One reviewer, a famous rheologist, candidly said ” ...my mind is not able to bend around your ideas. My upbringing was influenced by the classical concepts of Rouse, Graessley, de Gennes, etc, so it is difficult for me to understand and agree with some of your ideas...”. Kuhn’s criteria #1

 

A second reviewer, PhD, MBA, advisor to Coorporate Research Companies, approved the necessity of a change of paradigm in polymers and expressed enthousiastically the industrial perspectives of the sustained-orientation technology, he wrote:

 

“...with this new cross-dual phase model, Dr Ibar is able to explain the physics of polymer molecules, and particularly the rheology, and entanglement and disentanglement behaviours.

 

But he also added:”This book is not for the faint-hearted. It is both a complex, difficult read, and yet at the same time, exciting-brimming over with new concepts and ideas, almost mind-bending! ” .Kuhn’s criteria #2.  The full review is available in Ref. 7.

 

A third reviewer, the former Dean of a well established German University Plastic Processing Department, might have not been aware that his response would be transparent to Kukn’s 3rd way of fighting a new paradigm: sabotage by deception. Obviously, the Devil had whispered in his ears and could be satisfied of his pupil! Kuhn’s criteria #3.

 

I invite you to read my rebuttal of the paper published by this 3rd reviewer in the Journal of Rheology (JOR) by clicking on the link below:

 

Rebuttal to H. Munstedt JOR paper “ Mechanical Pretreatment of Polymer Melts. Critical Aspects and new rheological investigations on a linear and a long-chain branched Polypropylene”, J.O.R, 65.5(2021):871-885, DOI: 10.1122/8.0000237


Not only do I rebute one by one the various misrepresentations left uncorrected in this Journal, but I explain the difference of interpretations of Shear-Refinement of polymer melts by the classical views (orchestrated by the 3rd reviewer) and by the New School Polymer Physics’ approach to viscoelasticity.


Tell me:

 

-        Why would a scientist of great notoriety, publishing in a reputable science journal, need to deliberately publish false information to undermine the credibility of new research contradicting his convictions?  Why would he, the former Dean of his Department, denigrate the results by misquoting them, even a few times by deliberately distorting the facts? What was his real intention in using deception to disqualify the credibility of the results presented in a book1 he had accepted to review (and had accepted to discuss with the author)?

 

-        Why would the prestigious Journal not invite the discriminated author of the book as one of the reviewers of Munstedt’s paper when he submitted it? Is it not customary and fair to offer an author attacked in a paper to become a reviewer of the paper?

 

-        Why would the Editorial Board members of the Journal in which the notorious Professor published the deception stay mute when they were made aware of a rebuttal request by the author?  Even if it is true that the deception was disguised, subtle, and not apparent at first glance, the deception was revealed explicitly in the rebuttal article (now published as GJSFR A22.5(2022):21-31), documenting that it was not a divergence of opinion, that the author of the deception knew the facts but deliberately chose to misquote or distort them.  The peer review system can only be fair if it remains uncompromised.

 

Is it not obvious that the real reasons to disparage my work on the shear-induced melt instability of linear polymers (resulting in “disentanglement”, see Ch. 4 of my book1) is to avoid the discussion on the failure of the molecular models to comprehend it (Chs. 6, 7) and the need for a change of paradigm in polymer physics to understand entanglements (Ch. 1, 2).

 

And is it not true that the Editorial Board Members of the Journal were all siding with the notorious author to defend the current paradigm that my book claimed was deficient?

 

QED: KUHN’S ARGUMENT # 3 : “SABOTAGE  BY DECEPTION TO PREVENT ITS DISSEMINATION” IS THE REASON FOR H. MUNSTEDT’S FALSE INSERTIONS.

 

Here is how I concluded my letter sent to the Board Members of the journal ( Journal of Rheology) who found futile reasons to refuse to print my rebuttal:

 

“It is crucial that scientists doubt the results of others and it is of course acceptable to disagree with someone else‘s conclusions, but it is unacceptable to use deception to refute what one disagrees with”.

 

President Biden said recently (paraphrasing):

 

“It is the end of Democracy, yes the end of Democracy… if the contestants in an election only accept to win and accuse the winner of fraud if they lose.”

 

Likewise, it is the end of Science if the people in charge of disseminating and protecting the scientific method of enlightenment only accept to protect the existing paradigms and accuse the contradicting data of artifacts, even of fraud.

 

It is the end of the power of Science if the people in charge of disseminating and protecting the scientific method of enlightenment are systematically and deliberately censor-shipping the publication of results that prove the failures and short-comings of the established paradigms to cover- up the possibility that they are incomplete or simply wrong!

 

Yes, it is the end of the credibility of Science if the people in charge of disseminating and protecting the scientific method of enlightenment are accepting the insertion of unanswered false information in their publications and the use of deception tactics in their peer review administration. 

 

SHOULD SCIENCE STAY OUTSIDE MY REACH, THEN? ....pleaded the Devil...

 

1 Ibar J.P., “The Physics of Polymer Interactions. A Novel Approach. Application to Rheology and Processing”., HANSER (2019).

 

2. Ibar J.P., “Dual-Phase Depolarization Analysis: Interactive Coupling in the Amorphous State of Polymers”. REFERENCE book , Dual-Phase Polymer Science and Technology, De Gruyter (2022).

 

3. Ibar J.P. , “Dual-Phase Rheology. A New Understanding of Viscoelasticity in Polymers.” De Gruyter Book (2023)

 

4. Ibar J.P. ” Dual-Phase Crystallization. Dissipative Interactive Coupling between the amorphous and Crystalline states.”, De Gruyter Book (2024).

 

5. Ibar J.P. ” Grain-Field Statistics of Dissipative Interactions”, De Gruyter’s Book (2025)

 

6. Kuhn T. S. ” The Structure of Scientific Revolutions”, University of Chicago Press, 3rd Edition (1996).


7. Hutley T. ” REVIEW of Ibar’s book “The Physics of Polymer Interactions. A Novel Approach. Application to Rheology and Processing”., HANSER (2019).


8. Rebuttal to H. Munstedt JOR paper" Mechanical Pre-Treatments of Polymer Melts" 2021) 


vendredi 27 août 2021

IS THE LIQUID-LIQUID TRANSITION (TLL) FUNDAMENTAL?


YES, I do suggest that this transition, TLL, is fundamental in physics!

 I just published (Vol. 60 issue 10, Oct. 2021) a couple of papers about this subject of TLL, its existence and its impact (Part I and Part II):  Taylor and Francis has decided to publish it as a single volume of the J. Macromol. Sci. Physics.:


        Part I of the paper on TLL


         Part II of the paper on TLL


 Here are the Titles of the papers and their Abstract. 



ABSTRACT (Part I)


R.F. Boyer recognized the manifestations of a T > Tg transition-relaxation as early as 1963 and named it TLL, the liquid-liquid transition. He suggested that it was due to the melting of “local order”, a controversial issue conflicting with the dominant theories at the time, led by P. Flory, which asserted a structure-less liquid state for melts. At the same time as this controversy unrolled, de Gennes published his reptation model of polymer physics which, after some modifications and ramifications, quickly became the new paradigm to describe the dynamic properties of polymer flow. The new model of reptation has no theoretical arguments to account for a T > Tg transition occurring in the melt; hence, the current consensus about the existence of TLL is still what it was already in 1979, that it is probably an artifact only existing in the imagination of Boyer. In part I of this paper on the TLL transition, we mathematically derive the existence and the characteristics of TLL from a dual-phase description of the free volume using a modification of the Vogel-Fulcher equation (VF), a well-known formulation of the temperature dependence of the viscosity of polymer melts. This new expression of the VF formula, that we call the TVF equation, permits to determine that TLL is as an iso-free volume and iso-enthalpic state when M varies. The data analyzed by the TVF equation are the dynamic rheological results for a series of monodispersed, un-entangled polystyrene samples taken from the work of Majeste. The new analysis also permits to put in evidence the existence of a new transition, which we call Mmc, approximately located at Mmc ~ Mc/10, where Mc is the molecular weight for entanglement. A Dual-Phase interpretation of Mmc is proposed. 



ABSTRACT (Part II)

In Part I of these 2 parts paper we derived mathematically the existence of a unique state for polymeric melts, occurring at a specific temperature above Tg, which we recognized to be the liquid-liquid transition, TLL, observed and described by Boyer and others. TLL is the temperature at which the melt is in an iso-free-volume and iso-enthalpic state independent of the molecular weight. It is a fundamental property of the material. The purpose of part II is to examine and explain the following: 1. the elusive character of TLL (at the origin of the controversy about the existence of TLL in the past), 2. the increase of free volume at TLL and 3. the endothermal change of heat capacity on heating across TLL. Finally, our objective is to provide an explanation of TLL and emphasize its importance as an example of a self-dissipative dynamic process that converts, at TLL, into a classical thermally activated process. In this paper the experimental evidence found in the literature for TLL is critically examined to point out the often biased reviews offered by the antagonistic authors of a controversy, here the pros and cons TLL. We propose a Dual-Phase origin of the interactions in polymers to explain the weak and elusive manifestations of TLL and show, by DSC, that the TLL manifestations are made much more visible and prominent when the samples’ state has been brought out of equilibrium. We analyze, in detail, the thermally activated depolarization of samples which have been submitted to a polarization stage by a voltage field. The experimental technique of thermal stimulated depolarization (TSD), and its sister derivative the thermal-windowing-deconvolution (TWD), are unique and powerful analytical tools that can experimentally characterize “interactive coupling”, the factor that we have assumed is quantitatively responsible for the behavior of polymers and in particular of TLL. The existence and the characteristics of TLL were understood and predicted in Part I from rheological results by the use of the Thermo-Vogel-Fulcher equation whose thermo-kinetic terms, H, S and T, could be interpreted by the interactive coupling of the local free volume and the rotational isomeric conformational state of dual-conformers belonging to the macromolecules, themselves embedded in a collective dissipative system of interactions. The statistics controlling the interactive coupling parameters was described by the Dual-Phase and Cross- Dual-Phase models. In part II, the same models are used to explain the interactive coupling manifestations specific to the TSD and TWD results. We show that certain characteristics of the TSD and TWD results are directly related to specific parameters of the Dual-Phase model. It is the case for the transitions visible by TSD, such as Tg, related to space charges and local free volume (F-conformers), and TLL marking the end of the specific impact of the Dual-Phase statistics on the properties. It is also the case when interactive coupling is analyzed by TWD: the compensation of the enthalpy and entropy of activation of the relaxations taking place at various polarization temperatures only occurs below TLL, permitting its specific determination. 


We conclude pointing out the perhaps crucial importance of TLL in establishing the distinct role of thermal energy in structuring or modulating the dynamics of the interactions. The Dual-Phase view of the interactions in polymers suggests that the local density difference between the b-grains and the F-conformers is “time-averaged” by the constant wiping (above Tg) of an “elastic dissipative wave” having a frequency, , that is a function of temperature and molecular weight, and thus is different from the Brownian dissipation, i.e. the thermal fluctuation characteristic of the Boltzmann’s mean field (the classical kT/h term). The elastic dissipative wave kinetically loses its collective modulation role and becomes the thermal wave at TLL.


CONCLUSION

Is TLL the manifestation of a fundamental transition between the applicability of the Boltzmann’s statistics description of the interactions (mean average homogeneous field) and the Grain-Field Statistics’ description of the interactions (open dissipative systems generated by field fluctuations leading to dual and cross dual phases), the Grain-Fiel statistics being more general?

According to this interpretation of TLL and of its impact on the flow properties, the reptation and other polymer chain dynamic models can only provide valid predictions of the properties when T > TLL with TLL varying with molecular weight, pressure, shear rate etc. Unfortunately, without even knowing it, the experimental parameters used are often such that T < TLL, rendering invalid the applicability of the currently polymer dynamic models of rheology. Therefore, knowing the value of TLL during processing should play a major role in our ability to predict and control the properties of processed polymers.