Glucose can be obtained by hydrolysis of starch and detected as a reducing sugar by a heated alkaline copper(II) test. A positive copper test alone does not uniquely identify glucose.
Suspend starch in water, warm it to make a paste, and heat with a dilute acid, such as dilute sulfuric acid, to cause hydrolysis of the glycosidic bonds. The chemical reaction passes through shorter carbohydrates; sufficient hydrolysis ultimately gives glucose. The usual repeat-unit accounting is
This idealized polymer formula omits end-group details. The acid catalyses cleavage and is not consumed in the displayed equation. Merely using amylase from malt should not be described as necessarily producing pure glucose; it can leave maltose and shorter polysaccharides.
When sulfuric acid is used, neutralization with calcium carbonate removes the acidity and much of the sulfate as calcium sulfate. Filter out the insoluble residue, then concentrate the chemical solution gently and crystallize the glucose; further recrystallization is required to distinguish a reasonably pure chemical substance from a crude syrup. Overheating and unnecessarily prolonged strong acid treatment degrade the sugar. Hydrolysis of sucrose is a less selective preparative answer because it gives fructose alongside glucose.
For the historical copper test, use freshly mixed Fehling's reagent: an aqueous copper(II) sulfate portion and an alkaline tartrate portion. The tartrate keeps copper(II) in coordination complexes instead of allowing immediate bulk precipitation of copper(II) hydroxide. Add a suitably prepared sample to a small test portion and warm in a hot water bath. A yellow-orange to brick-red precipitate of copper(I) oxide indicates reduction of the copper(II) reagent. Run a known glucose sample and a water blank alongside it. In a simple sample, a visible difference between these controls helps distinguish a true positive from a deteriorated reagent or contamination.[ref]
The key redox accounting on the copper side is
The required electrons come from oxidation of the sugar. This half-equation deliberately omits the changing tartrate ligands and does not assign a unique organic product. The often printed claim that hot alkaline glucose simply becomes gluconate in this test is too simple: competing isomerization, oxidation and fragmentation make the organic chemistry more complicated.[ref]
Fructose, lactose, maltose and various other reducing substances can also give a positive Fehling's test. In particular, fructose can form aldoses by tautomerization in alkaline solution; an initial ketone functional group does not make it reliably negative.[ref] Fermentation by suitable yeast, with carbon dioxide formation, and optical rotation can supply further historical evidence, but neither is individually specific to glucose. These are anticipated diagnostic observations, not measurements supplied by the paper. In present laboratory practice an appropriately validated enzymatic glucose assay can establish glucose more selectively; the old reducing-sugar test is not by itself a diagnosis of diabetes.[ref]
For a polymer curve parameterized by contour distance , let be its unit tangent. The persistence length is the characteristic contour distance over which tangent orientations lose correlation. In the usual three-dimensional worm-like chain convention,
where is the bending stiffness. Segments much shorter than look approximately straight; a much longer chain can contain many statistically distinct orientations.
A surface image can be traced to estimate tangent correlations as a function of contour separation, after accounting for tracing resolution and substrate effects. A strictly equilibrated two-dimensional chain has a different relation between bending stiffness and correlation decay length from the three-dimensional convention. The definition must therefore state whether the surface preserves a projected conformation or allows in-plane equilibration. This is a statement about statistical filament mechanics; biological interpretation is deferred.
Use steric stabilization: attach or strongly adsorb a dense layer of polymer chains or compatible ligands, with tails well solvated by the nonpolar liquid. Overlap of these layers costs osmotic and conformational free energy and prevents particle cores reaching the strongly attractive contact region. The anchoring groups must bind the particle while the exposed chains prefer the solvent; sufficient coverage and a good solvent are essential. Nonpolar media do not make charging impossible, but electrostatic stabilization there requires an appropriate ion-generation and charge-stabilization mechanism, rather than assuming aqueous dissociation behaviour.
Adsorbed or grafted polymers stabilize a colloid through steric stabilization when coverage is high and the solvent keeps the chains extended. Charged chains can add electrostatic repulsion, giving electrosteric stabilization.
They can destabilize it through polymer bridging flocculation when a chain adsorbs onto two particles, especially at incomplete coverage; through depletion force when nonadsorbing polymer is excluded from the gap and the surrounding solution's osmotic pressure pushes particles together; or through collapse of an adsorbed layer in a poor solvent. Polymer identity, molecular size, solvent quality, adsorption and concentration determine which mechanism dominates.
For this self-assembly into a colloidal crystal, four useful elements are building blocks, interactions, environment and reversible dynamics. The building blocks here are nearly monodisperse polymer spheres; their shape and size distribution constrain the accessible packing. Their interactions include excluded volume, Van der Waals forces and electrostatic or steric stabilization, which set the free energy landscape. The aqueous environment supplies temperature, viscosity, ionic strength, confinement and concentration controls. Finally, Brownian motion and rotation must let particles encounter one another and rearrange or detach from incorrect contacts. Attractions that bind every collision irreversibly favour an amorphous aggregate rather than an annealed colloidal crystal. These four categories include both thermodynamic selection and the transport/kinetic access needed to realize it.
Flocculation indicates that the attraction/kinetic balance has changed: electrolyte may screen a double-layer barrier; pH may reduce surface charge; multivalent ions can promote aggregation; added polymer can bridge particles or cause depletion force; poor solvent conditions can collapse stabilizing layers. Rapid evaporation concentrates both particles and salts and can force contacts faster than they anneal. Aggregates then sediment much faster because their effective buoyant size has grown.
Check ionic strength, pH, surface charge and the particle size distribution before and during assembly. Dialyse or reduce salt where appropriate, restore surface charge, add a nonbridging steric stabilization with a compatible solvent, and slow the concentration step. Compare untreated and deliberately salt-screened controls. Restoring repulsion after irreversible aggregation may not redisperse the particles, so prevention is preferable to assuming all settled material can be recovered.
Three credible architectures are a welded silver nanowire network; a thin silver nanowire network with a conducting polymer overcoat; and a nanocrystalline silver grid formed from nanoparticle ink. Silver provides low intrinsic resistivity. A sparse long-wire network can be both flexible and highly transmitting if its junctions are well connected. A thin, optically weak conducting polymer overcoat can bridge junctions and smooth the surface, provided its added absorption and moisture sensitivity are controlled. A fine grid offers a more directly designed optical/electrical trade-off and does not rely on operating near random percolation.
For a quantitative grid feasibility screen, take pitch , line width and metal thickness . An opaque-line square-grid estimate gives . With a transmitting polymer substrate of 0.95, the combined estimate is 0.912. The sheet resistance is approximately . Even an effective silver resistivity four times gives , with a coating thinner than 400 nm. There are about 20 mesh periods across the stripe, making the finite-width design more credible than a pitch comparable with its whole width.
These are feasible material/process choices, not guaranteed specifications for every film carrying those names. For the two nanowire architectures, choose wire dimensions, loading and junction treatment to pass the same finished-stripe measurements; the hybrid's optical budget must include its overcoat. Measure transmission at 550 nm with its reference stated, sheet resistance, profile thickness, bend-cycle stability and pattern continuity. Bare nanotube or graphene networks should not be assumed to meet this demanding resistance–transmission combination without additional metallic conduction or other demonstrated improvement.
For the silver nanowire network, synthesize or source long, narrow wires, remove excess ligand without causing aggregation, formulate a stable coating ink and coat the flexible web by a scalable method such as slot-die coating or gravure printing. Dry below the substrate's damage temperature, then press or locally weld junctions and embed or cap the network if required. Define 100 µm stripes by masked coating, a printing-compatible patterned wetting layer, or post-coating laser ablation; provide robust end contacts and remove stray bridges between adjacent stripes. Roll processing offers throughput, but coffee-ring effect, wire alignment, random weak links and ablation damage require inline optical/electrical inspection. Verify that the local junction treatment improves resistance without simply darkening the whole film.
For the silver nanoparticle-derived grid, use a repeatable nanoimprint lithography to form a fine mesh inside the outer 25 mm by 100 µm stripe pattern. Fill the channels with a silver nanoparticle ink, remove excess from the transparent openings, and consolidate the metal by substrate-compatible chemical, photonic or low-temperature thermal sintering. Transfer or embed the grid into the polymer surface and add electrical pads. The quantitative design in part (b) sets target pitch, line width and thickness; the large-scale process must maintain those dimensions and a continuous metal cross section. A master enables repeated replication and deterministic open area, but tooling cost, incomplete filling, residual metal in windows, shrinkage cracks, imperfect sintering and adhesion are important limitations. Test the finished patterned stripes, rather than relying on a large unpatterned test coupon alone.
In a polyol process, a hot polyol such as ethylene glycol acts as solvent and reductant for a silver precursor. Nucleation creates seeds; controlled reduction supplies atoms for their subsequent growth, while polyvinylpyrrolidone adsorption and seed crystal twinning favour anisotropic growth. For the common silver nanowire route, a fivefold-twinned seed can develop into a pentagonal wire with predominantly side faces and growth at less-passivated ends. Cross-sectional microscopy and diffraction of microtomed wires provide evidence for that twinned structure rather than an inference from a long outline alone.[ref]
The aspect ratio depends on seed population and twin survival, relative end/side growth rates, precursor feed and reduction rate, PVP coverage, temperature, trace halides, dissolved oxygen and growth time. High aspect ratio requires a suitable population of twinned seeds, suppression of competing particle nucleation and continued atom supply while sidewall thickening is restrained. These variables must be controlled together; adding more capping polymer alone is not a universal recipe. Advantages are solution processing, substantial yield and tunable dimensions without an etched hard template. Disadvantages include sensitive batch reproducibility, particle by-products, residual insulating ligand, purification, oxidation/tarnish and nanowire junction resistance in later films. Compare seed/capping/halide controls using microscopy and size distributions, not only solution colour.
In the imposed free-draining polymer friction model, the drag coefficients of the monomers add, giving and . Taking the same three-dimensional centre-of-mass RMS convention as part (ii),
The polymer is a one-dimensional connected contour, but that alone does not restrict its centre of mass to one spatial axis. If the intended coordinate is instead literal one-dimensional curvilinear motion along an entanglement tube, its RMS contour displacement is . That is a different coordinate and should not be compared with a three-dimensional displacement without stating the conversion/model.
Additive local drag is the free-draining Rouse model approximation. It neglects long-range solvent-mediated hydrodynamic interactions and is not a complete theory of an entangled chain. In a tube/reptation description, curvilinear diffusion can scale as while long-time spatial centre-of-mass diffusion scales as after the chain renews its tube. Conversely a dilute unentangled coil can exhibit Zimm model hydrodynamic coupling. Monomer motion, centre-of-mass motion and contour sliding therefore cannot all be identified with the same displacement law.
The Flory interaction parameter measures the effective free energy penalty for unlike A–B contacts relative to like contacts, and is the total number of statistical segments per chain. Their product is the segregation strength: contact-energy preference competes with the conformational entropy cost of separating covalently joined blocks. does not grow during solvent evaporation. For an approximately nonselective solvent, increasing polymer concentration instead increases the effective importance of A–B contacts, so a roughly fixed-composition path moves from weak toward stronger effective segregation.
The diagram's labels are DIS: disordered; S: block-copolymer sphere phase; H: hexagonal cylinder block-copolymer phase; G: double gyroid; L: lamellar microphase. At , A is the minority component and B forms the continuous matrix. Reading the supplied diagram vertically at this composition gives disorder initially, a sphere region when segregation first becomes sufficient, and a cylinder region if sufficiently strong segregation is reached within the displayed range. The thin gyroid and central lamellar regions are not the thermodynamic equilibrium path at this composition. The dry endpoint cannot be fixed numerically without the final value. The cited theoretical calculation determines thermodynamic equilibrium phase stability, not a universal evaporation trajectory.[ref]
Crucially, at least one block is glassy at room temperature. Solvent can initially plasticize it, but solvent loss can raise its effective glass-transition temperature above the processing temperature. Chain relaxation then becomes too slow to equilibrate. Even slow evaporation can therefore freeze disorder, spheres, cylinders or another transient morphology before the thermodynamic equilibrium dry state is reached. Solvent concentration, annealing time and segmental mobility must be followed alongside the phase diagram.
A polymer melt has an observation-time-dependent response because chains need time to rearrange. Short compared with their terminal relaxation time, entangled chains constrain one another and can store elastic free energy. Long compared with that time, chains escape their original constraints by reptation and the uncrosslinked melt flows. A permanently crosslinked elastomer instead retains a long-time elastic modulus.
A single-time approximation is the Maxwell fluid: a spring of shear modulus and a viscous dashpot of viscosity in series. Their common stress and additive shear strains give , with relaxation time . For sinusoidal deformation proportional to , the storage modulus and loss modulus are
At low frequency dominates; at high frequency within this coarse-grained model dominates. Real melts have a spectrum of relaxation times and additional segmental or glassy regimes, so the single-time model does not describe every frequency. A step-strain experiment measures the decay of stress, whereas oscillatory rheometry separates stored energy from dissipated energy through the phase of the response.
The three solvent conditions describe effective interactions between segments of a generic polymer. In a good solvent, solvent contacts favor a swollen, self-avoiding coil with positive excluded volume. At a theta solvent condition, leading pair repulsion and attraction cancel; the chain has approximately ideal random-walk statistics. In a poor solvent, effective attraction contracts the chain, eventually producing a dense polymer globule for a sufficiently long chain.
For statistical segments of length , the radius of gyration has the scaling
The good-solvent power is the Flory approximation; the asymptotic three-dimensional exponent is closer to . In the ideal freely jointed chain, the more precise result is , whereas the end-to-end mean square is . Scaling notation suppresses those geometry-dependent factors. The globule power follows from a volume proportional to , and presumes a dense collapsed state away from the theta crossover. The dilute condition excludes overlap with other chains; it does not eliminate contacts between distant segments of the same chain.
Use polymer volume fraction horizontally and the Flory interaction parameter vertically. Lower gives better solvent quality. The simplest Flory–Huggins solution theory assigns the dimensionless mixing free energy per lattice site
Thus gives positive excluded volume and a good-solvent coil, is the long-chain theta condition, and is the poor-solvent side. It is the net two-segment interaction that vanishes at theta, not every molecular force.
At fixed good-solvent quality, the polymer overlap volume fraction separates isolated coils from a semidilute polymer solution. Above overlap, many chains interpenetrate, but there is still solvent on the segment scale. As approaches order unity the solution is concentrated; these concentration-regime boundaries are crossovers, not first-order phase transitions. The overlap fraction increases from order in a strong good solvent toward order at theta. The crossover can be expressed as while ; it saturates at the theta scaling when that condition fails.
On the poor-solvent side there can instead be coexistence of polymer-poor and polymer-rich phases. The binodal follows a common tangent of ; the spinodal follows
The critical point of a Flory–Huggins polymer solution is
For finite , lies above . Therefore poor solvent does not automatically mean demixing at every concentration, and an overlap line must not be mistaken for a coexistence boundary. The original figure uses the stated ideal model for an illustrative chain length; it does not assert a measured phase boundary. A vertical temperature axis would additionally require a material-specific relation .
The coil-globule transition is the contraction of an isolated flexible polymer as solvent quality worsens. A swollen chain in a good solvent has size in the Flory approximation. At the theta temperature the effective two-segment excluded volume vanishes and . A poor solvent favors a dense polymer globule, with at fixed internal density.
The competition is visible in the scaling free energy
For , elastic cost balances two-segment repulsion to give the swollen-coil law. At , three-segment repulsion stabilizes ideal-chain scaling; for , attraction balanced by the positive three-segment term gives . The dense polymer globule also has an interfacial free energy. The scaling expression explains regimes, not all fluctuation corrections or a detailed finite-chain transition curve. A finite chain crosses over smoothly; the sharp theta-point limit refers to indefinitely long chains.
A dilute-solution light-scattering experiment can follow radius of gyration while changing temperature or solvent composition. Measure at several concentrations and extrapolate toward isolated chains; check molecular-weight distribution, reversibility and the absence of growing multi-chain aggregates. dynamic light scattering measures hydrodynamic size, which is related to but distinct from radius of gyration. A falling scattering-derived size accompanied by a rising aggregate population cannot by itself establish single-chain collapse. solvent quality controls conformation through the balance of segment interactions and conformational entropy.
Interpret the stated free energy as per lattice site of volume . Flory–Huggins solution theory counts polymer chains, giving the entropy term , and solvent molecules, giving . The interaction term penalizes unlike contacts when ; a simple contact model has . Connectivity reduces polymer translational entropy relative to independent monomers. This is an incompressible mean-field model with composition-independent for the calculations below.[ref]
Expanding the dilute osmotic pressure identifies the effective second virial coefficient. A good solvent has and positive excluded volume, promoting swollen chains. A poor solvent has , favouring contraction and potentially phase separation. The theta-solvent condition is in this long-chain mean-field description: the second virial term vanishes, but higher terms remain. For finite , this condition is not the exact critical point, which instead has .
Let . The osmotic pressure in Flory-Huggins solution theory is
Thus . For mass concentration and chain molar mass ,
osmometry uses a membrane permeable to solvent but retaining every polymer chain, at known uniform temperature. Extrapolate to zero concentration to remove interactions; the intercept gives the number-average molar mass. Aggregation, leakage of small chains, ions with a Donnan contribution, or a poor-solvent two-phase sample invalidate the simple molecular-weight interpretation.
The measured ratios give an exactly linear reduced-pressure fit:
The reduced osmotic-pressure intercept is . The data determine ; the measurement temperature is needed to convert this into an absolute molar mass. For an explicitly assumed room temperature , . The boxed expression is the general answer for an arbitrary experimental temperature.
Figure 1.
Original reduced-osmotic-pressure regression and its zero-concentration intercept
. Details.
The Stokes–Einstein relation connects thermal diffusion with dissipative mobility. For a dilute suspension of isolated rigid spheres of hydrodynamic radius in an unbounded Newtonian fluid of viscosity ,
where is translational drag coefficient, diffusion coefficient and absolute temperature. Stokes drag supplies under no-slip, continuum, low-Reynolds-number conditions. The Einstein diffusion relation is more general than that particular spherical drag law.
A short equilibrium argument explains the connection. Let a weak external potential exert force , so drift velocity is . The number flux is . A Boltzmann distribution has ; requiring zero equilibrium flux fixes . thermal fluctuations and viscous dissipation are therefore linked, rather than independent adjustable effects. The original theory also relates diffusion to measured random displacements.[ref]
On times long compared with momentum relaxation, an isotropic diffusing sphere has
single-particle tracking can measure the slope. Alternatively, dilute single-scattering dynamic light scattering measures a field correlation ; the corresponding intensity-correlation excess is proportional to . The scattering wavenumber and the distinction between field and intensity decay must be retained.
A Stokes-Einstein experimental consistency test independently measures temperature and solvent viscosity, uses a narrow distribution of inert spheres, checks decay rate proportional to or displacement variance proportional to time, and extrapolates toward infinite dilution. Subtract drift, account for wall-enhanced drag, and verify that aggregation is absent. Tracking additionally needs spatial calibration and correction for finite exposure and localization precision. At finite concentration, collective diffusion is not automatically the single-particle self-diffusion in the equation. A hydrodynamic radius is not generally identical to a polymer radius of gyration; nonspherical particles, slip or viscoelastic solvents require a different mobility model.
polymers at interfaces balance favorable surface contacts against lost conformational entropy and interactions among neighboring chains. At an attractive solid–liquid interface, an adsorbed polymer train consists of consecutive bound segments. An adsorbed polymer loop leaves the surface and returns to it, while an adsorbed polymer tail extends to a free chain end. A chain can contain all three, so adsorption does not imply a completely flattened molecule. Surface affinity, solvent quality, persistence length, chain length and concentration control the balance and the resulting segment-density profile.
Figure 1.
Original schematic of adsorbed trains, loops and tails, and the crossover from isolated grafted mushrooms to an overlapping polymer brush
. Details.
adsorption gains energy of order per bound segment but reduces the number of accessible chain configurations. Weak adsorption can be described through adsorption blobs whose thickness exceeds the statistical segment length; each blob loses an energy of order through confinement. Stronger attraction generally creates more contacts and a more compact layer, while loops and tails can still dominate its outer extent. A measurement of adsorbed mass alone therefore does not determine layer thickness or conformation.
End-grafted chains are different: their attachment is fixed at one end. At grafting density , the mean lateral spacing is . At low coverage the chains behave as isolated polymer mushrooms. The polymer mushroom-to-brush crossover occurs when . At higher coverage in a good solvent, crowding makes chains extend away from the surface. A free-energy balance per chain,
combines stretching entropy with repulsive excluded volume . Minimization gives , or
This is a scaling result with an undetermined order-one coefficient, valid for overlapping chains stretched below their contour length. In a compact poor-solvent layer, a roughly fixed internal polymer volume fraction instead gives .
Small-angle neutron scattering on end-grafted polydimethylsiloxane layers on porous silica has distinguished the good- and poor-solvent density exponents. The chemical system and scattering contrast matter: changing solvent quality should be separated from changing graft coverage, chain molar mass or adsorption strength.[ref]
An interface can also localize chains of a block copolymer when its blocks prefer different media. Such layers change interfacial tension and can stabilize dispersed droplets or particles through steric repulsion. Overlapping layers in a good solvent cost osmotic and conformational free energy; incomplete adsorption can instead produce polymer bridging between particles. Nonadsorbing chains can cause depletion attraction. Thus the presence of a polymer does not by itself guarantee stabilization.
In a regular solution, ideal combinatorial entropy competes with a nonzero unlike-contact energy. For equal molecular volumes and mole fraction of species A, write mixing free energy per site as
where
Here is the coordination number and a pair-contact energy counted consistently in the lattice model. A positive penalizes unlike contacts; a negative value favors them. The logarithmic terms lower free energy on mixing. The sign of the enthalpy of mixing alone therefore does not determine miscibility.
At fixed temperature and composition, a homogeneous phase is globally stable only if no division into two compositions lowers its free energy. The common-tangent construction selects coexisting compositions , equivalent to equality of both species' chemical potentials. Local stability to infinitesimal fluctuations instead requires
Zero curvature gives the spinodal, while the coexistence boundary is the binodal. Between them a homogeneous state can be metastable and require nucleation; inside the spinodal its small composition fluctuations grow. The symmetric regular solution has
Below this contact penalty, the free energy is convex at every composition. Above it a miscibility gap is possible around the central composition. If with , heating promotes mixing, but specific interactions or temperature-dependent noncombinatorial terms can produce other trends.
For two polymers, let count equal-volume segments per chain, and now let be the segment volume fraction of A. Connecting segments into chains reduces their independent translational entropy. The binary Flory-Huggins polymer blend has
The energetic contact term remains extensive in the number of segments, while the favorable entropy per segment is reduced by and . This is the key long-chain limit of polymer-blend miscibility: a small positive incompatibility can overcome the mixing entropy. The lattice treatment is a controlled model for this argument, rather than a claim that every real blend has composition-independent .[ref]
The local stability condition and critical interaction parameter become
For equal chain lengths, . Similar segment chemistry and matched cohesive interactions can reduce the unlike-contact penalty; favorable specific interactions, such as complementary hydrogen bonding, can make mixing favorable even for long chains. Lower molar mass increases mixing entropy. temperature can help when it lowers the effective , but heating is not universally sufficient. A suitable common solvent can facilitate processing or ternary mixing, and a block-copolymer compatibilizer can stabilize fine domains; neither guarantees that the final solvent-free binary material is one equilibrium molecular phase.
An oil–water emulsion illustrates emulsion stability versus molecular miscibility. A surfactant adsorbs with its water-affine head toward water and its oil-affine tail toward oil, lowering interfacial tension and the work needed to make additional interface. Breaking a fixed oil volume into spherical droplets of radius gives total area , so creating small droplets still requires substantial area and usually mechanical work.
Adsorbed surfactants can oppose droplet coalescence through charged double-layer repulsion, hydrated-head interactions or steric repulsion from sufficiently extended groups. Adequate coverage, adsorption time, ionic conditions and film drainage affect the lifetime. A lower interfacial tension does not itself remove the bulk miscibility gap, and a protected emulsion is commonly kinetically stabilized. A thermodynamically stable microemulsion is a distinct situation requiring an appropriate composition and free-energy balance. The two liquids must not be called molecularly miscible simply because droplets disperse visibly.
For the capillary, balance upward contact-line force against hydrostatic column weight, neglecting meniscus volume and gas density. For inner radius ,
The contact angle is measured through the liquid. complete wetting means , so the contact-angle change of capillary rise gives
This follows from the stipulated wetting change, holding radius, bulk liquid surface tension and density fixed. One should not replace that premise with a general claim that grease always improves glass wetting; if contamination also changes the liquid surface tension, the original height and new angle alone would not determine the new height.
For two wide vertical plates separated by gap , use unit width. There are two upward contact-line contributions and liquid cross-sectional area , giving the capillary rise between parallel plates:
Only one principal meniscus curvature contributes between wide plates, whereas a circular tube has two. For the same fluid and angle,
If the plate gap equals the tube diameter, , the rise is half as large: the initial and completely wetting heights would be cm and cm. If instead , the heights are equal. In either geometry, changing only the angle from to zero multiplies the height by . Since the question specifies no plate spacing, the general gap-dependent relation is the unambiguous result; the half-height answer requires the equal-gap-to-diameter convention.
The Flory interaction parameter measures the excess cost of unlike segment contacts. In a simple lattice with coordination number , contact energies and temperature ,
A positive Flory interaction parameter penalizes unlike contacts; a negative value favors them. Mixing still depends on the balance with entropy of mixing, rather than the sign of alone.
For two polymers of degrees of polymerization , let be the volume fraction of species . The binary Flory-Huggins polymer blend has mixing free energy per lattice site
The logarithmic terms favor mixing. Their factors and arise because an entire chain translates as one object; connecting many segments greatly reduces the mixing entropy per segment. Hence long polymers can demix for a much smaller positive Flory interaction parameter than small molecules.
For composition-independent , the local stability criterion is
Positive curvature means stability to small composition fluctuations, zero curvature locates the spinodal, and negative curvature means spontaneous growth of fluctuations. Actual two-phase coexistence is determined by the common-tangent construction, or equality of both species' chemical potentials; its boundary is the binodal. A locally stable but globally unfavourable homogeneous mixture can lie between the binodal and spinodal.
Setting the second and third derivatives of to zero gives
For the symmetric Flory-Huggins polymer blend, and . For a polymer solution with and long chains of species , , consistent with the theta solvent limit. An effective Flory interaction parameter can depend on temperature and composition; in the simple energetic case , heating encourages mixing, but that temperature trend is not universal.
Figure 1.
Increasing the Flory interaction parameter can destroy stability of a symmetric polymer blend
. Details.
The original illustration uses stipulated . At the mixing free energy is convex, whereas at a central unstable region appears. The horizontal common-tangent construction in the latter case joins the symmetric coexisting compositions; its contacts differ from the spinodal boundaries. These are model curves, not supplied experimental data.