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date: 14 June 2021

# Chapter 1 The science of softness

• Tom McLeish

### Abstract

‘The science of softness’ provides a brief history and overview of soft matter science. The development of soft matter science was propelled by a combination of communication within the scientific community; intrinsic conceptual overlap and commonality; and visionary leadership from a small number of pioneering scientists. Chemistry proved as essential an ingredient to the new science of soft matter as ideas and techniques from physics. The characteristics of soft matter include motion; structure on intermediate length scales; slow dynamics; and universality. Microscopy is the most obvious and direct example of experimental tools applied across the gamut of soft materials.

Lucretius, the Epicurean poet and philosopher of the 1st century BC, wrote a remarkable compendium of natural history (De Rerum Natura—On Natural Things), which introduces the power of conjecturing that all substances are composed of tiny, invisible ‘atoms’, or ‘seeds’:

Wine, we see, will flow on the instant through a sieve, but oil is hesitant and slow, either because its particles are larger, or else more hooked and tightly intertwined, and this is why they can’t be pulled apart so quickly into separate single atoms that seep through single openings, one by one.

The Epicurean tradition sought to explain the observable properties of material things as arising from the structure of their atoms. Though centuries before the experimental and theoretical methods of modern science provided incontrovertible evidence of the existence of atoms, and the larger and more complex molecules which they build, the ancient atomists had grasped a fundamental explanatory key to the world.

Lucretius, and others of the school such as Democritus, were particularly interested in the behaviour of matter as it deforms and flows. The sluggishness of honey is a visible clue, pointing to the invisible and underlying nature and interaction of its atoms. Whether human observers reflected scientifically on it or not, the technology of pliant and deformable matter has an even longer history than the atomic hypothesis. The inks used by the Babylonians of antiquity and the rubber latex of ancient Central America are as indicative of intriguing material properties as the wine and honey of classical Rome.

The Epicurians were also correct in suggesting that flow properties of materials are pointers to their underlying structures. Heraclitus, a much older pre-Socratic philosopher, is credited with the aphorism ‘everything flows’ (Greek, panta rhei—παντα ρει‎) as a metaphor for the continual dynamic change inherent in matter. The Greek for flow, rhein, has given us the name for the science of flow and deformation, rheology. The different rates at which fluids flow under the same force—the sluggishness of honey and the quickness of water—was, for the ancients, and is in today’s experimental laboratories, the fundamental characteristic of soft materials. Rheology has now been transformed into a highly quantifiable tool, accompanied by modern techniques such as microscopy and light scattering that allow direct visualization of the tiny structures within its materials of interest. ‘Soft stuff’, by definition, deforms and flows; hence rheology has also become part of the broader interdisciplinary field of soft matter that has emerged over the past three decades.

Soft matter science is special. It begins with the commonplace and familiar, yet it can take us to the frontiers of the exotic unsolved. Who would suspect that the slow drip of the hevea tree’s latex would connect to the 20th century’s theoretical physics of ‘field theories’? Or that the discovery of carbon-based inks in the ancient world would lead, via the work of a botanist peering at the constant motion of particles within plant seeds, to Einstein’s work on heat and to the final convincing proof that atoms exist? Who would have guessed that the ancient discovery of soap-making would lead to an understanding of the self-assembled structures of the cells in living organisms themselves? This Very Short Introduction concerns deep ideas that pick up momentum on timescales of centuries yet also constitute some of the great cultural threads of our own time. The science of soft materials brings new insights into the world we see, hear, and feel around us. The lustrous whiteness of milk, the colourful swirls on soap bubbles, the stringy stickiness of melted cheese, the extraordinary extensibility of rubber, the switchable states of ‘liquid crystal’ displays—these everyday wonders may be familiar, but it is quite another thing to understand them. Such immediate sense impressions have nevertheless always been the starting point for science, so it will be those familiar properties that set the narrative of this book: the phenomenon of ‘soapiness’ leads to the science of ‘self-assembly’ and the experience of ‘sliminess’ to the idea of giant ‘polymer’ molecules (Figure 1 shows some different examples of soft matter, together with microscopic images of their underlying structures).

From the 1990s onwards, terms such as ‘soft matter’ and ‘soft matter physics’ began to appear with increasing regularity in conference announcements, review articles, and books. The new language reflected a cohering of previously much more fragmented scientific communities. ‘Soft matter’ had begun to subsume sciences that had previously gone by the names of ‘colloid physics’, ‘polymer physics and chemistry’, ‘liquid crystal science’, and more. The new term indicated not simply a merging of research programmes but that the whole represented more than the sum of those parts—the recognized emergence of a new field of science that drew on shared conceptual and experimental foundations. So materials falling under the labels of ‘colloids’, ‘polymers’, ‘liquid crystals’, ‘self-assembly’, ‘membranes’, ‘foams’, ‘granular materials’, ‘biological materials’, ‘glasses’, and ‘gels’ now find a common scientific home. Conversations between these sub-fields as well as within them are in consequence now commonplace.

Another contribution to the emerging history of soft matter science has been made by fruitful engagement between industries and universities. Many pioneering individuals have held posts in both, and many ideas and discoveries had their origin in industrial, rather than academic, laboratories. In the case of the science of plastics, for example, Du Pont in the USA and ICI in the UK were birthplaces for the synthesis of new materials and early theories of how the giant string-like molecules of ‘polymers’ are formed. Fundamental phenomena, for example the relation between the viscosity of melted plastic and the mass of their long-chain molecules, have often been first observed in industrial conditions. Even use of beams of sub-atomic neutrons—the technique known as ‘neutron scattering’—to elicit the first polymer structures was driven from these large industrial laboratories. Soft matter has illustrated how the fields of technology and science are far more closely entangled than the common phrase ‘technology transfer’ would suggest.

Furthermore, the nature of experiment and ways of theorizing in soft matter raises profound questions of where ‘fundamental’ scientific ideas really lie. The American physicist and Nobel Laureate Philip Anderson, in a landmark article entitled ‘More is Different’ published in the 1970s, described how structures can ‘emerge’ at length scales much greater than those of atoms and molecules, but which are just as ‘fundamental’. Soft matter provides many illustrations of Anderson’s claim that the notion of fundamental physics should not be tied to any one scale of length or energy, and that while ‘reductionism’ (the explanation of the behaviour of a system purely in terms of that of its smallest constituents) is an essential tool in science, it cannot be the whole story of how we understand the world. Nature is built from many components, but fundamental novelty arises also from the way they are assembled hierarchically. A few dozen atoms can build small molecules, which can in turn be assembled into giant ‘macromolecules’ or ‘nanoparticles’, whose properties now depend not on their tiny building blocks but on their shape and structure as a whole.

The development of soft matter science was propelled by a combination of communication within the scientific community (through conferences, research departments, and journals that attracted scientists from more than one sub-field), intrinsic conceptual overlap and commonality, and visionary leadership from a small number of pioneering scientists. Pre-eminent among those were two theoretical physicists working in the latter half of the 20th century, Pierre-Giles de Gennes in France (later a Nobel Laureate in physics), and Sir Sam Edwards in the UK. Both realized that broad conceptual frameworks and powerful theoretical techniques from other areas in physics could be applied to soft matter systems, and that as a result, simple and deep structures could be perceived beneath what had previously seemed a disparate collection of very complicated materials. The conceptual leaps were considerable: ideas from fields dominated by the structures of quantum mechanics required translation into systems dominated by thermal physics, whose tools and techniques appear at first sight to be quite distinct. The background of Edwards (a former student of American Nobel prizewinner Julian Schwinger) was quantum field theory—the physics of interaction of light with matter; while de Gennes (a former student of French physicist Jacques Friedel) had worked on superconductivity—the bizarre phenomenon of zero electrical resistance that appears in some metals at very low temperatures. The theoretical models they forged to describe the soft matter physics of polymers and liquid crystals respectively were written in the language of mathematics adapted from their earlier work, but the tangible soft matter examples opened up other, more visual and diagrammatic ways of understanding. These, rather than the formulas, will provide our conceptual ways into soft matter.

Chemistry proved as essential an ingredient to the new science of soft matter as ideas and techniques from physics, together with a renewed conversation between the two sciences. Chemists brought not only the careful synthetic construction of the remarkable giant molecules and assemblies of soft materials but also ways of thinking about and characterizing the subtle forces between them. Arising from ancient technology, the imaginative leaps of individuals, and the cross-fertilization of ideas—including the final opening of a window onto the atomic world itself, imagined for so many centuries—it is not possible to tell a convincing story of the science of soft matter without visiting some more of its history in each case study.

Before we take deeper dives into some specific examples of soft matter, telling their stories, opening the experimental windows into their structures, and the theoretical concepts that have begun to turn the familiar into the understood, we first need to think a little more about what we mean by ‘soft matter’ itself, anticipating a handful of characteristics that are shared by the materials we term ‘soft’ and the science used to investigate them.

### Characteristics of soft matter

The term ‘soft’ is used essentially in its everyday sense—but the compliance and mechanical subtlety of soft or weak solids, gels, and fluids is also the first clue to their internal structure and dynamics, for soft materials reflect a hidden inner world of constant motion.

### Thermal motion

The ancient notion of atoms, and its modern development into the variously structured molecules of gases, liquids, and solids around us, is a good starting point but not quite enough to explain or understand ‘softness’. One of the most astonishing demonstrations that molecular ingredients alone are insufficient to determine material properties requires a rose and a container of the extreme coolant: liquid nitrogen (the gas that, apart from the 21 per cent of oxygen, comprises most of the rest of the air we breathe, liquifies at about −200°C). The lustrous rose’s petals are indeed as ‘soft’ to the touch of a finger as any object we might imagine and as pliant. But now cool the flower to the temperature of the liquid nitrogen by submerging it in the nitrogen for a few seconds, and when we extract it by its stalk, while there is no visible change to its colour or shape, a sharp tap from a hammer will shatter the petals into so many shards, like a fragile piece of glass sculpture (see Figure 2).

The vital difference in the molecular structure of the flower at room temperature and at −200°C is not in the chemistry but in the motion of the molecules. Every one of these is in constant random motion, careering now in one direction, now in another, the chemical bonds between atoms vibrating and rotating this way and that. The higher the temperature, the faster all these motions are, on average, while instantaneous values of the random velocities vary hugely. This is the chaotic molecular motion that we call ‘heat’ on everyday scales.

The systematic study of this essential inner motion of matter was initiated by the early 19th-century botanist, Robert Brown, who published a landmark pamphlet on it in 1828. He described his efforts at understanding the source of a constant ‘jiggling’ motion and diffusion of small particles suspended within pollen grains he had observed through his field microscope. In humble, but highly responsible, fashion, Brown explained all the many possible causes of the ceaseless motion (from magnetism to currents in the fluid) that he had systematically ruled out, yet he still found himself unable to account for its source. Although the correct explanation had to wait for an equally seminal paper by Einstein in 1905, as we shall see in Chapter 2, the thermal agitation is rightly called ‘Brownian motion’.

Every part of every material is subjected to Brownian motion, but where strong bonds tie the molecules or atoms to each other, such as in metals or minerals, the random thermal motions will not be able to excite large changes in structure. Shaking a steel climbing-frame in the local playground causes only a slight vibration. But applying the same force to and fro to the climbing net made of rope on the next-door apparatus will cause it to fluctuate wildly. Likewise at the molecular scale, the thermal kicks that jostle molecules around will have a greater effect on those joined by more compliant and weaker bonds. Here lies the molecular key to understanding ‘softness’. Soft materials exhibit large local rearrangements of their microscopic structural constituents under thermal agitation, while ‘hard’ materials suffer only small distortions under the same effects of heat.

There is a way of turning this idea of fluctuations and distortions from random thermal motion into numbers—a measure of ‘softness of matter’. The great 19th-century German scientist Ludwig Boltzmann gave us the ‘currency conversion’ formula we need to translate a temperature T (on the absolute scale where zero is −273°C) into the typical thermal energy of motion ET that every microscopic particle will possess at that temperature. The ‘Boltzmann constant’ (a very small number when written in everyday units), written kB, provides the conversion factor: just like currency conversion from dollars into pounds, we simply convert temperature T into mean atomic energy ET using

$Display mathematics$

The higher the temperature T, the greater the mean energy of molecular motion E, delivering an increase of kB for every degree increased (depending on the structure of the molecule the increase may be a small multiple of this number). At ordinary temperatures this energy quantum belongs at the atomic scale, tiny in everyday human terms, but it is enough to send an oxygen molecule careering off at 300 metres (m) per second (s) at room temperature (this is therefore the average speed of the molecules in the air you are now breathing). Now we have the numbers, it becomes possible to determine if a piece of molecular matter is ‘soft’ or ‘hard’. We simply need to ask if the energy required to move each of its atoms and molecules when the material is twisted and deformed substantially (say more than by 10 per cent) is greater, or less than ET. This is the criterion that separates glass from the biological fabric of rose petals. But only at room temperature—Brown, Bolzmann, and others had laid the foundations of the temperature-dependent science of thermodynamics, which would prove indispensable to understanding soft matter.

### Structure on intermediate length scales

There are other recurring characteristics to soft matter beyond the essential ingredient of large thermal fluctuations in its structure. A significant one is simply located in the typical scale of important microscopic structures themselves. Recall how very small atoms are. If a bed bug were enlarged to the size of an Alpine mountain, then the atoms composing its leg would be the size of the original bed bug. There is therefore plenty of room at intermediate scales on which to build structures, between the size of atoms and everyday dimensions. The significant structures that determine the properties of soft matter are still tiny on human length scales yet are typically built from very large numbers of atoms. So these basic units we need to imagine in order to understand soft matter behaviour are neither ‘macroscopic’ nor truly ‘microscopic’ (in the atomic sense) but ‘mesoscopic’ (‘meso’ from the Greek word for ‘middle’). Structure between the length scale of several nanometres (1 nm = 10–9 m, or ten times the size of atoms) to a micron (m; a hundred times this) is almost ubiquitous in soft matter systems.

To give some examples: the giant string-like molecules of polymers are long chains consisting of many thousands, or even millions of atoms. Their flexibility means that, when dissolved in a solution, they adopt randomly contorted coils whose diameters are typically several tens of nanometres in scale, a thousand times the size of an atom. The particles and droplets suspended in the milky fluids we call ‘colloids’ are too tiny to see with the naked eye, yet they comprise typically millions of atoms. Liquid crystals are, as we shall see, solutions of rod-shaped molecules which locally tend to point in the same direction. For an analogy, think of combing flat the hair on a dog—at every point the hairs lie in the same direction (like the local orientation of molecules in a liquid crystal). The emergent patterns of molecular direction support ‘defect structures’—points or lines at which the local direction of molecular orientation suddenly changes. The behaviour of the liquid crystalline material is dominated in many ways by the mesoscopic length scale at which the defects interact (much larger in this case as well than the scale of the molecules themselves). The second images in each case of Figure 1 show schematically the different mesoscopic structures underlying the soft matter phenomena, matched panel for panel.

The dominance of these structural, ‘mesoscopic’ length scales in soft matter systems implies a crucial principle for understanding them. If their key structural components are themselves composed of thousands of atoms or more, then mathematical models for polymers or liquid crystals which attempt to keep track of all those atoms will not deliver insight into why they behave as they do. We sometimes say that appropriate models for soft matter systems need to be ‘coarse-grained’—if we are to understand them, the fine atomic details need to be blurred out, otherwise we do not ‘see the wood for the trees’. Here we encounter once more the central message of Anderson’s ‘More is Different’ manifesto—‘fundamental’ structures are not necessarily atomic or sub-atomic. In soft matter they are typically much larger. The chapters that follow will highlight in each case the mesoscopic structures and the coarse-graining of the models we use to describe them.

### Slow dynamics

The mesoscopic spatial scales of soft matter’s fundamental components implies another characteristic property of how they move. The dynamical behaviour of polymers, liquid crystals, and other soft matter examples can be as complex as their spatial structures. Complexity in time follows complexity in space. The component molecules are moving about in random thermal motion and colliding with each other at unimaginably short intervals (in dense fluids at room temperature, the mean thermal velocity of the order of 300 ms–1 dictates an average collision time of about a picosecond1 picosecond = 10–12 s). Yet the much larger mesoscopic structures of soft matter systems can possess ‘slow variables’ whose values change on much longer timescales. A common everyday example is found in foams—whether on top of glasses of beer or formed by soap froth in the washing up. The molecules within the films may be colliding on ultrafast microscopic timescales, but the foams themselves slowly rearrange and combine their cells, gradually draining away after seconds or even minutes. For another example, think of the ‘silly putty’ children’s toy. This remarkable material can be rolled up into a ball and bounced on the floor like rubber. Yet left on its own on a table top for a few minutes and it flows into a puddle. In other words, on short timescales the putty behaves like an elastic solid, while at longer scales it flows as a viscous liquid (we say that it is ‘viscoelastic’). Somehow it possesses an internal timescale—of seconds or minutes—that dictates whether it is behaving in its ‘fast mode’ (bouncing) or ‘slow mode’ (flowing). The slow flow of molten polymers, first observed in the industrial laboratories that developed early plastics, is another example of viscoelastic material behaviour.

### Universality

A sort of ‘super-property’ of soft matter arises from the characteristics we have already discussed—the high importance of thermal fluctuations, mesoscopic structures, coarse-grained physics, and slow dynamics. It is called ‘universality’, signifying that the same material properties in each class of soft matter can arise from many different underlying chemistries. So, for example, the elastic strength of a polymer rubber is dependent on the density and distribution of the cross-links between its constituent polymer chains, not on the chemistry of the chains themselves. What matters is that the polymer chains are physically connected and flexible; any local chemistry that delivers these characteristics will support a network with the same physical properties. Similarly, the ‘liquid crystalline’ fluids of rod-like molecules all pointing in the same direction appear whenever there are densely packed molecules of elongated shape, independently of the atoms from which they are built (there are special cases such as molecules possessing electric charges that can behave differently). This characteristic of universality is of immense practical relevance. Where it holds, solving a problem for one specific example can automatically solve it for whole families of materials. It is also of deep conceptual significance, since the understanding of a general phenomenon is usually more powerful than an insight restricted to a specific example.

### Experimental commonalities

The emergence of soft matter as a coherent field of study is by no means the result of theoretical ideas alone. The parallel growth of important experimental tools was also vital. Furthermore, these laboratory techniques also applied across the gamut of soft materials, in a similar way to the theoretical tools. Microscopy is the most obvious and direct example. Deceptively simple, there is a lot more to magnifying small structures than arranging a light source and some lenses lined up in front of them. For example, special techniques that collect the light emerging from just one specific plane in the object under study have overcome the confusion that otherwise presents an observer peering through many hundreds of layers of particles.

The same principles that guide optical microscopy can be applied to any wave-like probe of matter. One consequence of quantum mechanics is that all material ‘particles’ propagate as waves in a similar way to light. ‘Microscopies’ exist that exploit this ‘wave-particle duality’, of which the best known uses electrons to probe and image matter. Since electrons are charged particles, they may be focused by ‘lenses’ of electric and magnetic fields, and since their wavelengths are so much smaller than those of light, they can image far smaller details. Delicate structures in self-assembled membranes furnish an example of the details laid bare by electron microscopy (see Figure 1(c)).

The advantage of microscopy is its ability to reveal details of local structures within soft matter, but by the same token, its disadvantage is the consequent inability to sample and average such local detail across an entire sample. Finding information on averages is important when the mesoscopic structures are random—like the coiling polymer chains or the constantly rotating and diffusing rod-molecules of liquid crystals. A family of techniques that performs just such an integrative view is known as ‘scattering’. Like microscopy, anything that propagates as a wave—light, X-rays, and also particles such as electrons and neutrons all make good scattering probes, depending on the materials under study. We will have more to say about scattering in Chapter 3, but here note the general geometry of an incoming beam striking a sample, which ‘scatters’ radiation across an arc of angles into an array of detectors (illustrated in Figure 13 in Chapter 3). An analogy of the beam might be the bowler/pitcher in a game of cricket/baseball, the fielders representing the array of detectors. Even without a visible view of the game, the frequency with which the ball is picked up by each fielder alone contains information about the batter, for example whether they are left- or right-handed.

Scattering experiments respond naturally to the scale of mesoscopic structure in soft matter. X-ray crystallographers have used the scattering of high-energy, short wavelength X-rays to resolve the tiny atomic spacings in crystals. Longer wavelengths of X-rays, cooler neutrons, or looking at smaller angles of scattering can all extend the same experimental idea to probe longer length scales than atomic spacing. These 10–100 nanometres scales are those in which the mesoscopic membranes of cell walls, the expanded coils of giant polymer molecules, or the gentle ordering of colloidal spheres (see Figure 1) all swim into view.

The feature of slow dynamical structures within soft matter motivates a further set of techniques to identify and characterize, common to soft matter, and which focus on the mechanical properties of the material. This is, after all, where the ‘softness’ comes from. Furthermore, there are complex connections between the structural changes at the nanoscale and the resultant flow properties of the bulk material. The corresponding techniques fall under the banner of the ‘rheology’ introduced at the start of this chapter, and the instruments that apply them are known as ‘rheometers’. The essential operation of a rheometer is to impose specific geometries of deformation, or ‘strain’, on a soft matter sample, and to measure the forces that the deformation induces on its surfaces.

A common example is depicted in Figure 3, showing the simple ‘shear flow’ of soft material or fluid constrained between two parallel plates. The lower is fixed, the upper moving with a velocity, either constant or oscillating to and fro at a range of frequencies.

The arrows in Figure 3 indicate the fluid velocities at different points in this shear flow. A shear rheometer will generate a small cell of material moving in this pattern and also measure the sliding forces on the plates necessary to maintain the flow. The ‘shear stress’ is this force per unit area of plate. Defined in this way, ‘stress’ becomes independent of the sample size, so it describes the internal properties of the material.

Since stress has, in principle, many components, corresponding to forces on the material surfaces both parallel to the flow and perpendicular to it, the rheology of soft matter can be richly complex. There is a historical and conceptual resonance with scattering experiments here: Karl Weissenberg invented one of the first rheometers for soft matter and called it a ‘rheogoniometer’ (reported in 1962), deliberately alluding to a moving detector device, or ‘goniomenter’ used in scattering experiments. As a former researcher on X-ray scattering from giant biomolecules, he conceived of rheology as a sort of scattering experiment—samples ‘received’ a range of geometries of strain and ‘scattered’ a range of geometries of stress out from its various surfaces, measured in an analogous way to detecting X-rays, light, or neutrons from a scattering experiment (as illustrated in Figure 13 on p. 52).

A sticky, stringy hot melt of a plastic, which flows as a liquid when trapped between the plates of a rheometer sliding slowly over each other, mimics the elasticity of rubber—it is viscoelastic—when the plates simply oscillate back and forth at high enough frequencies. Additionally, when a steady shearing flow rate on the same material is increased, its apparent viscosity reduces—it becomes a more runny liquid. This property, of great importance in processing for the plastics industry, is called ‘shear-thinning’. We will delve into the molecular reasons for both in Chapter 3.

A range of colloid fluids—those composed of tiny suspended particles—exhibit an opposite effect when the particles are very densely packed. While they behave as fluids at low flow rates, they may display a strong increase in effective viscosity as the imposed flow rate increases, leading in some cases to a liquid-to-solid-like transition. Stirred cornflour paste is a familiar example—under slow stirring it flows easily, but a vigorous turn of the wooden spoon can cause the entire bowl to solidify momentarily. Such ‘jamming transitions’ have only very recently been explained theoretically in terms of changes in the fluids’ microscopic structures (see Chapter 2).

Our introduction to soft matter science has already called on physics, chemistry, and engineering. More recent applications to the analysis of biological and bio-inspired phenomena increases the interdisciplinary palette even further. The consequences are as yet hard to predict, but already two promising directions for research have been generated. The first sheds new light on the physical basis of biological phenomena; the second draws inspiration from biology to define new research programmes in physics, chemistry, and materials engineering. An example is the rapidly growing field of ‘active matter’, the subject of this Very Short Introduction’s last chapter, Chapter 6. The pickings for historians and philosophers of science interested in the social functioning of scientific communities will I suspect prove very rich when a little more dust (some of it ‘active’) has settled.

Each of the chapters that follow explores one of the soft matter family of materials in more depth. The experimental tools of microscopy, rheology, and scattering of light and other wave-like radiation will crop up as we investigate each one. Likewise, the common features of thermal (or ‘Brownian’) motion, intermediate (or ‘mesoscopic’) structures, slow dynamical processes, and universality together create a conceptual framework. Looking out for each of these features in the milky world of colloids, the stringy space of polymers, the foamy fluids of self-assembled soft matter, and the light-play of liquid crystals will help to connect their initially very different appearance and behaviour. It will also uncover some marvellously simple ways of thinking deeply about materials that, although their science might be new, have played important roles in human culture and technology for centuries, even millennia.