Clean and degrease the nickel surface, remove its inhibiting oxide by an appropriate brief surface treatment, rinse, and immerse it in an aqueous bath containing reducible gold(III) species. Control concentration, temperature and immersion time, then rinse after the desired deposition. A solution of a gold complex is practical, but its actual reduction potential must be evaluated for that complex and bath: it need not equal the supplied free-ion standard potential.
At anodic sites nickel dissolves as , releasing electrons into the conducting substrate. Those electrons reduce gold ions at cathodic sites, nucleating and growing metallic gold. The nickel itself is the reducing agent, so no external electrical supply or separate reducing reagent is required. The coupled electron balance is three nickel atoms dissolved for two gold atoms deposited for the stated oxidation states.
The process can slow or stop when a sufficiently continuous gold coating prevents the electrolyte from reaching nickel. This is not an absolute thickness rule: pores, cracks or exposed edges preserve nickel dissolution and allow continued deposition, sometimes with undercutting. nickel passivation, depletion of gold ions near the surface, diffusion through a porous layer, bath speciation and competing reactions also affect the rate. Dense gold coverage and porous gold coverage therefore have very different limiting behavior.
A pyroelectric material has a spontaneous electric polarization that changes with temperature. electrodes collect the resulting change in compensating charge. For a uniform element,Consequently temperature variation in time, rather than a steady temperature difference alone, drives a pyroelectric generator. A cyclic thermal input and a suitable electrical circuit are needed for repeated energy extraction.
The primary pyroelectric effect is the change of electric polarization at fixed strain. The secondary pyroelectric effect arises because thermal expansion strains a piezoelectric crystal and thereby changes its electric polarization. In component notation its contribution iswith piezoelectric coefficients and thermal-expansion coefficients . Choosing orientation, mechanical constraint and substrate expansion so that the secondary contribution reinforces the primary one can increase the response; the signs can instead oppose one another.
An array of slender nanowires can expand more freely than a film clamped to a substrate and can exchange heat rapidly because of its high surface-to-volume ratio. Reduced clamping can recover a secondary response suppressed in the film. Faster thermal cycling can also increase electric current through . This is a geometrical opportunity rather than a universal increase of the intrinsic coefficient: screening, leakage, orientation and the actual thermal excursion must be compared. ZnO nanowire generators provide an experimental realization of pyroelectric energy conversion.[ref]
Pyroelectric nanogenerators for harvesting thermoelectric energy by Ya Yang and others. Abstract: vertically aligned ZnO nanowire arrays used for pyroelectric generation
A thermocouple uses two materials with different Seebeck coefficients. With their junctions at different temperatures, the net open-circuit voltage isUsing p-type and n-type legs makes the two contributions add. Many pairs can be connected electrically in series to add voltage while remaining thermally in parallel between the same hot and cold plates. A single homogeneous wire does not provide this same complete-circuit voltage when its return lead has the same thermopower.
The reciprocal Peltier effect transports heat when electric current passes through a junction. The Kelvin relation connects the heat carried per unit charge to the Seebeck coefficient. The same combination of large thermopower, high electrical conductivity and low thermal conductivity gives a favorable dimensionless figure of meritThus materials useful for a generator are also useful for a cooler when electric current is driven in the appropriate direction. Joule heating and thermal leakage oppose cooling; device geometry, contact resistance and operating temperature must still be appropriate. Reversibility of the thermoelectric coupling does not make either device lossless.
Taking room temperature as , the thermal voltage is . For the stated ideal diode, , soThe term is negligible here. A different precise interpretation of room temperature changes the result noticeably because of the exponential; the calculation above states its temperature explicitly.
For a lower-bandgap material, the intrinsic carrier concentration generally rises, increasing the reverse saturation current density, approximately through with when other parameters are held comparable. Thus the forward electric current at the same voltage would normally increase. If were artificially held fixed at the supplied numerical value, however, the ideal-diode equation would give the same electric current: the band gap dependence enters through the material parameters rather than as a separate term in that equation.
Rolling graphene into a single-walled carbon nanotube quantizes the circumferential wave vector, leaving a set of one-dimensional longitudinal subbands. At each subband edge the group velocity tends to zero, producing a Van Hove singularity in the density of states. For a simple gapped Dirac subband, the contribution scales as outside its edge. At low temperature the valence states below the Fermi level are occupied and the conduction states above it are empty. A semiconducting tube has a gap; an ideal metallic tube has gapless channels as well as higher-subband singularities.
For light polarized along the tube, the strongest allowed interband transitions connect corresponding subbands while approximately conserving axial wave vector and circumferential angular momentum. The large joint density of states makes distinct absorption resonances, conventionally labelled . Strong electron–hole interactions produce bound excitons, so the observed optical resonances differ from the noninteracting band separations. Defects, doping, bundling and dielectric screening change peak energies and oscillator strengths. The original schematic below depicts the subband-edge structure, not measured spectra.
Let be the liquid-minus-solid free energy density at the same temperature. Near the bulk coexistence temperature , linearization givesFor a sphere, an interface displacement changes area and volume with . Equality of the bulk driving force and the capillary cost at a curved solid–liquid interface therefore gives . Equivalently, differentiating gives the same stationary radius. Combining the expressions yieldsThis form of the Gibbs-Thomson effect assumes isotropic interfacial energy, a spherical interface, bulk-like latent heat per volume and a near-coexistence free energy expansion. More detailed free-particle models must distinguish solid–vapor, liquid–vapor and solid–liquid energies.
Prepare size-characterized gold-particle ensembles, heat them on a calibrated in-situ electron diffraction stage, and follow the loss of sharp fcc diffraction features and appearance of liquid-like diffuse scattering. Measure the particle size distribution rather than treating a polydisperse ensemble as one diameter. Temperature-dependent weakening of a diffraction peak alone is insufficient: thermal vibrations, particle motion, coalescence, evaporation and beam damage can also reduce intensity. Low-dose repeats, heating/cooling runs, size checks before and after heating, a bulk-like reference and support-dependent controls help distinguish melting from those effects. Electron diffraction measurements on gold particles down to about 2 nm are a classic demonstration.[ref]
Size effect on the melting temperature of gold particles by Ph. Buffat and J-P. Borel. Physical Review A 13 (1976), pp. 2287–2298, abstract: scanning diffraction and size-distribution analysis
The physical origin is the large interface contribution to free energy at small radius. A curved solid–liquid interface raises the solid's thermodynamic equilibrium chemical potential relative to the flat-interface case, so coexistence occurs below the bulk melting temperature. Reduced coordination and surface disorder provide a microscopic interpretation, but the quantitative continuum relation is a free energy balance, not simply a claim that every surface atom has a universal lower melting point.
In terms of diameter , the model isThus melting temperature rises toward the bulk value as diameter increases, with a depression proportional to . The analytic sketch below includes the calculated point. It deliberately does not extrapolate the continuum expression down to a zero or negative melting temperature.
Facet-dependent energies, non-spherical shapes, size-dependent interfacial energies and latent heat, structural changes or magic cluster sizes can modify the trend. Premelting can broaden the transition. A substrate or encapsulating matrix changes interface energetics and can stabilize or destabilize the solid. Ligands, impurities, strain, particle size distributions, coalescence during heating and nonequilibrium temperature/beam effects can shift the measured transition. These possibilities motivate separate thermal, structural and size controls rather than a fit to diameter alone.
The map shows Coulomb blockade with discrete single-electron charging: low-current diamonds separate charge-stable regions from finite-bias transport windows. A small conducting island or quantum dot must be tunnel-coupled to source and drain, with a gate shifting its electrochemical potential. Charging prevents sequential transport until an island addition/removal energy enters the bias voltage window.
The tunnel resistances should substantially exceed the resistance quantum , preventing charge fluctuations from washing out integer island occupancy, while still permitting a measurable current. Temperature and tunnel broadening must be small compared with the addition-energy scale. Here the smaller diamonds imply , so , or ; resolving the inferred 1 meV orbital structure requires the stricter scale . Stray capacitance and unintended multiple islands can complicate this simple interpretation.
Write the descending and ascending switching fields as and . The exchange bias loop centre and magnetic coercivity half-width areWith exchange bias, a field-cooled bilayer has , often a shift opposite to the cooling field for the conventional negative-bias case shown in the diagram. The sign is not universal; it depends on interfacial coupling and preparation. A simple rigid-pinning estimate is .
Cooling farther below the blocking range usually strengthens antiferromagnetic anisotropy and suppresses thermal relaxation, so the magnitude of the shift and often the coercive width grow. Close to or above the blocking temperature the shift disappears; the blocking temperature can be below . Repeated cycling can rearrange interfacial spins and reduce the bias, and the two reversal branches can acquire different shapes. Thus increasing low-temperature asymmetry is a common tendency, not a guaranteed monotonic law for every interface.
Increase particle volume fraction slowly by controlled evaporation or gentle concentration until ordering becomes favourable, while preserving sufficient colloidal repulsion to prevent irreversible sticking. Hard-sphere-like monodisperse suspensions can crystallize by packing entropy; weak, reversible attractions can also favour ordered assembly if they allow defect correction. A controlled drying front or patterned surface may guide the orientation, and gentle sedimentation can create a concentration gradient that crosses the ordering range.
The practical requirement is slow structural change relative to Brownian motion, with uniform temperature, well-characterized ionic strength and a narrow size distribution. An abrupt salt addition or rapid drying can remove the repulsive barrier and trap aggregates instead of growing a crystal. Scattering or microscopy should distinguish crystalline peaks/order from merely increased turbidity.
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.
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]
Polyol Synthesis of Uniform Silver Nanowires: A Plausible Growth Mechanism and the Supporting Evidence by Yugang Sun and others. Nano Letters 3 (2003), pp. 955–960, pentagonal cross sections and fivefold twinning
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.
For a no-slip spherical particle in a Newtonian fluid at low Reynolds number, Stokes law gives . The fluctuation-dissipation theorem then gives the Stokes–Einstein relation . Using the conventional radial Brownian displacement in three dimensions,Here is the Boltzmann constant, absolute temperature, dynamic viscosity, particle radius and elapsed time. Larger thermal forcing raises diffusion; larger viscous drag reduces it. The formula requires times long relative to momentum relaxation and neglects walls, interactions and external drift.
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]
Stability of the Gyroid Phase in Diblock Copolymers at Strong Segregation by Eric W. Cochran and others. Macromolecules 39 (2006), pp. 2449–2451, equilibrium diblock phase stability
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.
The integer quantum Hall effect requires a conducting two-dimensional electron gas with well-resolved Landau levels. In the simple parabolic-band model their orbital spacing isLow temperature and sufficiently low disorder broadening are needed so that and the relevant level width are small compared with this spacing. A high-mobility sample with is therefore useful.
Some disorder has a constructive role: localized states between extended Landau-level states allow the Fermi energy to move through a range of carrier populations while the transport response stays on a plateau. The longitudinal response is then very small and the transverse response is quantized. Whether odd or only even integer plateaux are resolved also depends on whether spin splitting is resolved.
Absorption converts part of the incident optical power into heat. Increasing laser power can therefore raise the local temperature, potentially driving a thermotropic nematic liquid crystal through its nematic-isotropic transition. The associated loss or change of orientational order, refractive index and anchoring can alter the trapping force or destabilize the trap.
Even below that transition, thermal gradients can induce convection, thermophoretic drift and changes in viscosity or Brownian fluctuations; sufficiently strong heating can damage the particle or host. Thus increasing laser power need not simply strengthen an otherwise unchanged optical trap.
Past exam of the MPhil in nuclear energy course of the University of Cambridge 2019 Module NE4 2026-10-20
Original worked solutions cover all four printed alternatives. The University of Cambridge release occupies physical PDF pages 17–20; the questions are on pages 18–20. [ref]
https://www.whatdotheyknow.com/request/past_exam_papers_16/response/2088673/attach/3/FOI%202022%20471%20Smith%20materials.pdf?cookie_passthrough=1#page=17. Original public PDF, physical pages 17–20
The glass-release plot is an illustrative model, and the materials arguments state when reversibility, crystallographic texture, temperature or exposure history changes the conclusion.
thermal cycling growth is permanent dimensional change remaining after a temperature cycle; irradiation growth is a radiation-driven change of shape that need not require an applied load. Neither is simply the reversible increase in dimensions of a warm specimen.
For a crystal in its principal axes, a small unconstrained thermal strain isanisotropic thermal expansion means that the principal components of differ. Adjacent crystal grains with different orientations therefore demand different strain tensors during the same temperature change. Their bonded boundaries impose compatibility and generate internal stresses. plasticity, creep, boundary motion or microcracking can accommodate this mismatch irreversibly; when the accommodation fails to cancel on cooling, a residual strain remains. Repeated cycles can accumulate directional thermal ratcheting, surface roughening or distortion. crystallographic texture, constraints, cycle amplitude and the temperature dependence of yielding and recovery determine the outcome.
Anisotropy alone is insufficient. A freely expanding single crystal under spatially uniform, fully reversible heating returns to its original dimensions. Even cyclic plasticity can settle into a stabilised response rather than ratchet indefinitely. Demonstrating thermal cycling growth means comparing dimensions at the same reference temperature after successive cycles, while controlling external loads, temperature gradients and phase changes. uranium dimensional instability under cycling was investigated directly in the early reactor-materials programme.[ref]
Thermal Cycling of Uranium by Nathaniel Stetson and Melbourne L. Winton. ORNL-1386, 1952, opening discussion of dimensional instability, preferred orientation and observed distortion
irradiation growth has a different source of irreversibility. displacement cascades create vacancies and self-interstitials; anisotropic migration, clustering and capture at oriented dislocations and boundaries can produce unequal strains along crystal directions. For approximately volume-conserving growth,although a rod may elongate substantially in one direction. The effect can occur at constant temperature without an external stress. Distinguish it from void swelling, which increases volume through cavities, and irradiation creep, whose directional deformation is stress-dependent. Experiments should therefore measure axial and transverse dimensions, density and the applied stress rather than identifying every increase in length as one mechanism.

